4,12-Diselena-5,6,13,14-tetra­aza­tri­cyclo­[9.3.0.03,7]tetra­deca-1(11),3(7),5,13-tetra­ene

Schollmeyer, D.; Detert, H.

doi:10.1107/S2414314625003244

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 5| May 2025| x250324

https://doi.org/10.1107/S2414314625003244

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4,12-Diselena-5,6,13,14-tetraazatricyclo[9.3.0.0^3,7]tetradeca-1(11),3(7),5,13-tetraene

Dieter Schollmeyer ^a and Heiner Detert ^a ^*

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

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 8 April 2025; accepted 10 April 2025; online 2 May 2025)

In the title compound, C₈H₈N₄Se₂, two almost planar 1,2,3-selenadiazoles are annulated to a cycloocta-1,4-diene with a boat–chair conformation, giving the molecule a butterfly shape.

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

CCDC reference: 2442669

Structure description

The title compound, C₈H₈N₄Se₂, was prepared as part of a project focusing on medium-sized cycloalkynes with additional sterically demanding groups (Bissinger et al., 1988 ; Detert et al., 1994 ; Detert & Meier, 1997 ). Bis-1,2,3-selanadiazoles are important sources for medium-sized cycloalkadiynes (Gleiter et al., 1988 ) and the structure of an isomer of the title compound has recently been reported (Detert & Schollmeyer, 2020 ). The tricyclic molecule adopts a butterfly-like shape with a boat–chair conformation of the eight-membered ring and two 1,2,3-selenadiazole rings are fused to the central ring (Fig. 1). Selenadiazole ring 1 (C2—N3—N4—Se5—C6) is planar within 0.003 (3) Å and selenadiazole ring 2 (C10—N11—N12—Se13—C14) within 0.008 (3) Å. While the connecting C1 atom lies above the plane of both selenadiazole rings [selenadiazole 1: 0.130 (3) Å; selenadiazole 2: 0.118 (3) Å], the adjacent C atoms of the propylene tether are either above these planes [C7: 0.037 (3) Å] or below [C9: −0.134 (3) Å]. The planes of the selenadiazole rings subtend a dihedral angle of 79.64 (13)°. Strain in the medium-sized ring is reflected in distortion of the bond angles on C7 [113.8 (3)°], C8 [115.8 (3)°] and C9 [118.4 (3)°], whereas a bond angle of 108.3 (2)° for C2—C1—C14 is close to the perfect tetrahedral angle. The packing diagram of the title compound is shown in Fig. 2.

Figure 1
View of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Figure 2
Part of the packing diagram, viewed along the a-axis direction.

Synthesis and crystallization

The title compound was prepared from cyclooctane-1,4-diol via Jones oxidation, formation of the semicarbazone and reaction with selenous acid in a 4.4% overall yield [m.p. 398–400 K (decomposition)]. Crystals were grown by slow evaporation of a solution in chloroform–propan-2-ol. ¹H NMR (400 MHz, CDCl₃): δ 5.01 (s, 2H, H₂C-2), 3.25 and 3.10 (each: t, 2H, J = 6.6 Hz, H₂C-8,10), 1.95 (pseudo-q, 2H, H₂C-9). ¹³C NMR (100 MHz, CDCl₃): δ 159.4, 158.9, 156.4, 156.1 (C-1, 2, 7, 11); 26.7 (C-2), 26.4 (C-9), 25.7, 24.7 (C-8, 10) 41.5, 29.4, 28.5, 27.4, 25.5, 22.5, 20.0. ⁷⁷Se NMR (73 MHz, CDCl₃, SeO₂/D₂O as reference): δ 241.3, 240.7; UV (EtOH): λ (logɛ): 222 (4.09), 287 nm (3.45), MS (FD): 320 (M⁺, Se₂-isotope pattern), 292 (M⁺—N₂, Se₂-isotope pattern), 264 (M⁺—N₂, Se₂-isotope pattern).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to C atoms were placed at calculated positions and were refined in the riding-model approximation, with C—H = 0.99 Å and U_iso(H) = 1.2 U_eq(C).

Table 1
Experimental details

Crystal data
Chemical formula	C₈H₈N₄Se₂
M_r	318.10
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	7.2217 (4), 15.6664 (8), 8.4925 (5)
β (°)	90.110 (4)
V (Å³)	960.82 (9)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	7.66
Crystal size (mm)	0.42 × 0.31 × 0.21

Data collection
Diffractometer	STOE IPDS 2T
Absorption correction	Integration
T_min, T_max	0.107, 0.251
No. of measured, independent and observed [I > 2σ(I)] reflections	5404, 2296, 2066
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.071, 1.17
No. of reflections	2296
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.44
Computer programs: WinXpose in X-AREA (Stoe & Cie, 2020 ), Recipe in X-AREA (Stoe & Cie, 2020), Integrate in X-AREA (Stoe & Cie, 2020), SHELXT2014 (Sheldrick, 2015a ), SHELXL2019 (Sheldrick, 2015b ) and PLATON (Spek, 2020 ).

Structural data

CCDC reference: 2442669

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314625003244/vm4066sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625003244/vm4066Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314625003244/vm4066Isup3.cml

checkCIF report

Computing details top

4,12-Diselena-5,6,13,14-tetraazatricyclo[9.3.0.0^3,7]tetradeca-1(11),3(7),5,13-tetraene top

Crystal data top

C₈H₈N₄Se₂	F(000) = 608
M_r = 318.10	D_x = 2.199 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.2217 (4) Å	Cell parameters from 11184 reflections
b = 15.6664 (8) Å	θ = 2.7–28.3°
c = 8.4925 (5) Å	µ = 7.66 mm⁻¹
β = 90.110 (4)°	T = 120 K
V = 960.82 (9) Å³	Block, colorless
Z = 4	0.42 × 0.31 × 0.21 mm

Data collection top

STOE IPDS 2T diffractometer	2296 independent reflections
Radiation source: sealed X-ray tube, 12x0.4mm long-fine focus	2066 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.022
rotation method, ω scans	θ_max = 28.0°, θ_min = 2.7°
Absorption correction: integration	h = −9→8
T_min = 0.107, T_max = 0.251	k = −20→20
5404 measured reflections	l = −11→9

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.071	w = 1/[σ²(F_o²) + (0.0269P)² + 2.435P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max = 0.001
2296 reflections	Δρ_max = 0.48 e Å⁻³
127 parameters	Δρ_min = −0.44 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.

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

	x	y	z	U_iso*/U_eq
C1	0.4215 (4)	0.37887 (19)	0.9033 (4)	0.0160 (6)
H1A	0.302532	0.380853	0.960943	0.019*
H1B	0.522437	0.369867	0.980596	0.019*
C2	0.4515 (4)	0.46134 (19)	0.8159 (3)	0.0152 (6)
N3	0.6299 (4)	0.49038 (17)	0.7962 (3)	0.0178 (5)
N4	0.6528 (4)	0.55671 (18)	0.7130 (3)	0.0221 (6)
Se5	0.42162 (5)	0.59667 (2)	0.63795 (4)	0.02054 (10)
C6	0.3146 (4)	0.5069 (2)	0.7443 (4)	0.0157 (6)
C7	0.1118 (4)	0.4872 (2)	0.7445 (4)	0.0180 (6)
H7A	0.042450	0.539719	0.717557	0.022*
H7B	0.074926	0.469928	0.852125	0.022*
C8	0.0561 (4)	0.4161 (2)	0.6286 (4)	0.0185 (6)
H8A	−0.076361	0.423468	0.601538	0.022*
H8B	0.128039	0.423644	0.530446	0.022*
C9	0.0848 (4)	0.3240 (2)	0.6872 (4)	0.0171 (6)
H9A	0.039233	0.321004	0.796966	0.020*
H9B	0.004683	0.286199	0.623171	0.020*
C10	0.2770 (4)	0.2876 (2)	0.6847 (3)	0.0153 (6)
N11	0.3132 (4)	0.22323 (17)	0.5779 (3)	0.0175 (5)
N12	0.4723 (4)	0.18783 (17)	0.5841 (3)	0.0194 (5)
Se13	0.61533 (4)	0.23617 (2)	0.74477 (4)	0.01775 (9)
C14	0.4189 (4)	0.30689 (19)	0.7851 (3)	0.0141 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0178 (14)	0.0145 (14)	0.0158 (13)	0.0004 (11)	−0.0014 (11)	−0.0020 (11)
C2	0.0175 (14)	0.0135 (13)	0.0147 (13)	−0.0003 (11)	−0.0004 (11)	−0.0039 (11)
N3	0.0174 (13)	0.0166 (12)	0.0195 (12)	−0.0013 (10)	−0.0014 (10)	−0.0040 (10)
N4	0.0211 (14)	0.0207 (14)	0.0246 (14)	−0.0032 (11)	0.0018 (11)	−0.0046 (11)
Se5	0.02600 (18)	0.01483 (16)	0.02079 (16)	−0.00047 (12)	0.00078 (13)	0.00212 (11)
C6	0.0169 (14)	0.0152 (14)	0.0151 (13)	0.0011 (11)	0.0004 (11)	−0.0006 (11)
C7	0.0142 (14)	0.0180 (15)	0.0217 (15)	0.0037 (11)	−0.0019 (12)	−0.0011 (12)
C8	0.0120 (14)	0.0218 (16)	0.0217 (15)	0.0006 (11)	−0.0015 (12)	−0.0011 (12)
C9	0.0132 (14)	0.0198 (15)	0.0182 (14)	−0.0017 (11)	0.0005 (11)	−0.0005 (12)
C10	0.0157 (14)	0.0150 (13)	0.0152 (13)	−0.0011 (11)	−0.0002 (11)	0.0016 (11)
N11	0.0217 (13)	0.0156 (12)	0.0153 (12)	−0.0004 (10)	−0.0012 (10)	−0.0009 (10)
N12	0.0224 (14)	0.0193 (13)	0.0165 (12)	−0.0003 (11)	−0.0011 (10)	−0.0020 (10)
Se13	0.01585 (16)	0.01742 (16)	0.01997 (16)	0.00329 (11)	−0.00227 (11)	−0.00193 (11)
C14	0.0143 (14)	0.0125 (13)	0.0155 (13)	0.0007 (11)	0.0007 (11)	−0.0002 (10)

Geometric parameters (Å, º) top

C1—C2	1.506 (4)	C7—H7B	0.9900
C1—C14	1.510 (4)	C8—C9	1.540 (4)
C1—H1A	0.9900	C8—H8A	0.9900
C1—H1B	0.9900	C8—H8B	0.9900
C2—C6	1.362 (4)	C9—C10	1.501 (4)
C2—N3	1.377 (4)	C9—H9A	0.9900
N3—N4	1.268 (4)	C9—H9B	0.9900
N4—Se5	1.892 (3)	C10—C14	1.366 (4)
Se5—C6	1.842 (3)	C10—N11	1.382 (4)
C6—C7	1.497 (4)	N11—N12	1.277 (4)
C7—C8	1.540 (4)	N12—Se13	1.870 (3)
C7—H7A	0.9900	Se13—C14	1.833 (3)

C2—C1—C14	108.3 (2)	C9—C8—C7	115.8 (3)
C2—C1—H1A	110.0	C9—C8—H8A	108.3
C14—C1—H1A	110.0	C7—C8—H8A	108.3
C2—C1—H1B	110.0	C9—C8—H8B	108.3
C14—C1—H1B	110.0	C7—C8—H8B	108.3
H1A—C1—H1B	108.4	H8A—C8—H8B	107.4
C6—C2—N3	116.8 (3)	C10—C9—C8	118.4 (3)
C6—C2—C1	124.4 (3)	C10—C9—H9A	107.7
N3—C2—C1	118.6 (3)	C8—C9—H9A	107.7
N4—N3—C2	117.5 (3)	C10—C9—H9B	107.7
N3—N4—Se5	110.0 (2)	C8—C9—H9B	107.7
C6—Se5—N4	87.31 (13)	H9A—C9—H9B	107.1
C2—C6—C7	126.9 (3)	C14—C10—N11	115.4 (3)
C2—C6—Se5	108.3 (2)	C14—C10—C9	126.9 (3)
C7—C6—Se5	124.7 (2)	N11—C10—C9	117.6 (3)
C6—C7—C8	113.8 (3)	N12—N11—C10	117.5 (3)
C6—C7—H7A	108.8	N11—N12—Se13	110.5 (2)
C8—C7—H7A	108.8	C14—Se13—N12	87.40 (13)
C6—C7—H7B	108.8	C10—C14—C1	126.1 (3)
C8—C7—H7B	108.8	C10—C14—Se13	109.3 (2)
H7A—C7—H7B	107.7	C1—C14—Se13	124.6 (2)

C14—C1—C2—C6	83.3 (4)	C7—C8—C9—C10	−78.1 (4)
C14—C1—C2—N3	−91.8 (3)	C8—C9—C10—C14	74.3 (4)
C6—C2—N3—N4	−0.2 (4)	C8—C9—C10—N11	−110.8 (3)
C1—C2—N3—N4	175.2 (3)	C14—C10—N11—N12	0.7 (4)
C2—N3—N4—Se5	−0.1 (3)	C9—C10—N11—N12	−174.7 (3)
N3—N4—Se5—C6	0.3 (2)	C10—N11—N12—Se13	0.2 (3)
N3—C2—C6—C7	178.3 (3)	N11—N12—Se13—C14	−0.8 (2)
C1—C2—C6—C7	3.1 (5)	N11—C10—C14—C1	174.7 (3)
N3—C2—C6—Se5	0.5 (3)	C9—C10—C14—C1	−10.4 (5)
C1—C2—C6—Se5	−174.7 (2)	N11—C10—C14—Se13	−1.3 (3)
N4—Se5—C6—C2	−0.4 (2)	C9—C10—C14—Se13	173.7 (2)
N4—Se5—C6—C7	−178.3 (3)	C2—C1—C14—C10	−75.3 (4)
C2—C6—C7—C8	−78.4 (4)	C2—C1—C14—Se13	100.0 (3)
Se5—C6—C7—C8	99.1 (3)	N12—Se13—C14—C10	1.1 (2)
C6—C7—C8—C9	82.1 (3)	N12—Se13—C14—C1	−174.9 (3)

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