(10Z)-4H,5H,6H,7H,8H,9H-Cyclo­deca­[d][1,2,3]selena­diazole

Schollmeyer, D.; Detert, H.

doi:10.1107/S2414314624011076

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 11| November 2024| x241107

https://doi.org/10.1107/S2414314624011076

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(10Z)-4H,5H,6H,7H,8H,9H-Cyclodeca[d][1,2,3]selenadiazole

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 M. Bolte, Goethe-Universität Frankfurt, Germany (Received 13 November 2024; accepted 14 November 2024; online 19 November 2024)

The title compound, C₁₀H₁₄N₂Se, was prepared from a semicarbazone and selenium dioxide. The planes of the heterocycle and the cis double bond are almost mutually orthogonal and the hexamethylene tether is nearly strain-free.

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

CCDC reference: 2402782

Structure description

The title compound, C₁₀H₁₄N₂Se (Fig. 1), was prepared as part of a project focusing on medium-sized cycloalkynes (Bissinger et al., 1988 ; Detert & Meier, 1997 ). Thermolysis of 1,2,3-selenadiazoles is an advantageous route to strained cycloalkynes. They are prepared by oxidation of semicarbazones with selenium dioxide (Lalezari et al., 1972 ). Selenious acid oxidized Z-cyclodec-3-enone semicarbazone to a mixture of the title compound (63%) and the homoconjugated (5Z)-isomer. In the crystal, the molecules are arranged in layers parallel to the ac plane. Within a layer, all molecules adopt the same orientation, while in the neighbouring layers, the orientation of the molecules is inverted. The selenadiazole ring is essentially planar with an r.m.s. deviation of 0.002 (2) Å. In addition, the connecting atoms of the aliphatic tether are coplanar, C4 lies only 0.044 (2) Å above and C11 − 0.012 (2) Å below the selenadiazole plane. A negligible torsion angle [0.02 (4)°] twists the double bond (C10=C11) but the dihedral angle of 88.56 (15)° between the heterocycle and cis-olefin disrupts the π-conjugation. The hexamethylene chain shows a strain-free staggered arrangement. The packing is shown in Fig. 2.

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

Figure 2
Part of the packing diagram. View along the a axis.

Synthesis and crystallization

The title compound was prepared in 63% yield from the semicarbazone of (3Z)-cyclodecenone. The required ketone appeared in 10% yield upon selenious acid catalyzed hydrolysis/isomerization of (2Z)-cyclodecenone semicarbazone (Whitham & Zaidlewicz, 1972 ; Hirano et al., 1974 ). Selenium dioxide (2 mmol) was added to 0.5 mmol of the semicarbazone in 10 ml of 1,4-dioxane. After 3 days stirring, the solvent was evaporated, the slurry was mixed with toluene, washed with water, dried (MgSO₄) and the compound isolated via chromatography with toluene/ethyl acetate on silica gel. Yield: 63% of yellowish crystals with the typical fetid odor of selenadiazoles. NMR analysis at 298 K gave clear signals for the olefinic subunit but broad signals for the methylene chain, indicating constricted conformational interconversions on the NMR time scale. Only at very low temperatures did the diastereotopic protons e.g. at C-4 gave separate signals of good resolution. M.p. = 315 K. ¹H NMR (400 MHz, CDCl₃, 293 K): 6.27 (d, 1 H, J = 11 Hz, H—C-11), 5.88 (ddd, 1 H, J = J′ = 11 Hz, J′′ = 5.5 Hz, H—C-10), 3.05 (bs, 2 H), 2.96 (bs, 2 H), 1.74 (bs, 2 H), 1.48 (m, 4 H), 0.99 (bs, 2 H); (400 MHz, CDCl₃, 228 K): ; (400 MHz, CDCl₃, 228 K): 6.25 (d, 1 H, J = 11 Hz, H—C-11), 5.85 (ddd, 1 H, J = J′ = 11 Hz, J′′ = 5.5 Hz, HC-10), 3.18 (pseudo-d, 1 H, J = 14 Hz, H—CH-4), 2.78 (ddd, J = J′ = 14 Hz, J′′ = 4 Hz, HC—H-4), 1.95 (m, 3 H), 1.56 (t, J = 13 Hz), 1.42 (m, 1 H), 1.25 (m, 4 H), 0.58 (m, 3 H). ¹³C NMR (CDCl₃): 159.5 (²JC—Se = 32 Hz, C-3a), 155.1 (¹JC—Se = 130 Hz, C-11a), 138.9 (²JC—Se = 37 Hz, C-11), 119.9 (C-10), 26.8, 25.6, 24.9, 24.7, 20.9, 20.5 (C4 - C9). ⁷⁷Se NMR (CDCl₃): 221.2 UV–Vis (EtOH): 224 (2.93), 239 (3.49), 294 (3.41) nm (logɛ) IR (CDCl₃): 3005, 2920, 2840, 1495, 1430, 1310, 1255, 1210 cm⁻¹.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₁₀H₁₄N₂Se
M_r	241.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	7.9646 (6), 17.0830 (15), 8.0572 (6)
β (°)	111.425 (6)
V (Å³)	1020.50 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.64
Crystal size (mm)	0.29 × 0.21 × 0.11

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	Integration [X-RED32 (Stoe & Cie, 2020 ), absorption correction by Gaussian integration (Coppens, 1970 )]
T_min, T_max	0.381, 0.697
No. of measured, independent and observed [I > 2σ(I)] reflections	5508, 2430, 2093
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.067, 1.12
No. of reflections	2430
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.40
Computer programs: X-AREA WinXpose, Recipe and Integrate (Stoe & Cie, 2020), SHELXT2014 (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ) and PLATON (Spek, 2020 ).

Structural data

CCDC reference: 2402782

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314624011076/bt4160sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624011076/bt4160Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314624011076/bt4160Isup3.cml

checkCIF report

Computing details top

(10Z)-4H,5H,6H,7H,8H,9H-Cyclodeca[d][1,2,3]selenadiazole top

Crystal data top

C₁₀H₁₄N₂Se	D_x = 1.570 Mg m⁻³
M_r = 241.19	Melting point: 315 K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.9646 (6) Å	Cell parameters from 10316 reflections
b = 17.0830 (15) Å	θ = 2.4–28.4°
c = 8.0572 (6) Å	µ = 3.64 mm⁻¹
β = 111.425 (6)°	T = 120 K
V = 1020.50 (15) Å³	Block, colorless
Z = 4	0.29 × 0.21 × 0.11 mm
F(000) = 488

Data collection top

Stoe IPDS 2T diffractometer	2430 independent reflections
Radiation source: sealed X-ray tube, 12x0.4mm long-fine focus	2093 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.020
rotation method, ω scans	θ_max = 27.9°, θ_min = 2.4°
Absorption correction: integration [X-Red32 (Stoe & Cie, 2020), absorption correction by Gaussian integration (Coppens, 1970)]	h = −7→10
T_min = 0.381, T_max = 0.697	k = −21→22
5508 measured reflections	l = −10→10

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)] = 0.030	H-atom parameters constrained
wR(F²) = 0.067	w = 1/[σ²(F_o²) + (0.0224P)² + 1.2555P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
2430 reflections	Δρ_max = 0.41 e Å⁻³
118 parameters	Δρ_min = −0.40 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. Hydrogen atoms were placed at calculated positions and were refined in the riding-model approximation with C_aromatic–H = 0.95 Å or C_methylene–H = 0.99 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	0.22155 (3)	0.41792 (2)	0.00291 (3)	0.02588 (8)
N2	0.0679 (3)	0.42034 (14)	0.1321 (3)	0.0287 (5)
N3	0.1303 (3)	0.37734 (13)	0.2705 (3)	0.0242 (4)
C3A	0.2906 (3)	0.33871 (13)	0.3010 (3)	0.0200 (4)
C4	0.3665 (3)	0.29010 (14)	0.4674 (3)	0.0223 (5)
H4A	0.467261	0.257977	0.460615	0.027*
H4B	0.271954	0.254034	0.474213	0.027*
C5	0.4350 (3)	0.34033 (14)	0.6375 (3)	0.0227 (5)
H5A	0.331482	0.368148	0.650443	0.027*
H5B	0.486911	0.305438	0.741913	0.027*
C6	0.5776 (3)	0.40050 (14)	0.6379 (3)	0.0223 (5)
H6A	0.525551	0.434969	0.532727	0.027*
H6B	0.606410	0.433562	0.745666	0.027*
C7	0.7529 (3)	0.36533 (14)	0.6347 (3)	0.0231 (5)
H7A	0.836267	0.356584	0.758932	0.028*
H7B	0.725966	0.313698	0.574953	0.028*
C8	0.8476 (3)	0.41614 (15)	0.5396 (3)	0.0235 (5)
H8A	0.965934	0.392425	0.555708	0.028*
H8B	0.870326	0.468471	0.596223	0.028*
C9	0.7400 (3)	0.42610 (13)	0.3392 (3)	0.0217 (5)
H9A	0.626221	0.454180	0.322631	0.026*
H9B	0.810602	0.458548	0.286372	0.026*
C10	0.6965 (3)	0.34927 (15)	0.2428 (3)	0.0233 (5)
H10	0.794761	0.321303	0.231365	0.028*
C11	0.5350 (3)	0.31628 (15)	0.1718 (3)	0.0235 (5)
H11	0.527227	0.267070	0.114513	0.028*
C11A	0.3666 (3)	0.35080 (14)	0.1757 (3)	0.0200 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.01898 (12)	0.03822 (15)	0.01753 (12)	−0.00109 (10)	0.00322 (8)	0.00338 (10)
N2	0.0176 (9)	0.0410 (13)	0.0244 (10)	0.0014 (9)	0.0042 (8)	0.0008 (9)
N3	0.0153 (9)	0.0351 (12)	0.0216 (10)	−0.0003 (8)	0.0059 (8)	−0.0011 (8)
C3A	0.0165 (10)	0.0235 (12)	0.0198 (10)	−0.0040 (8)	0.0063 (8)	−0.0041 (9)
C4	0.0195 (11)	0.0246 (11)	0.0217 (11)	−0.0025 (9)	0.0061 (9)	0.0008 (9)
C5	0.0205 (11)	0.0279 (12)	0.0190 (11)	−0.0006 (9)	0.0063 (9)	0.0010 (9)
C6	0.0211 (11)	0.0243 (12)	0.0198 (11)	−0.0008 (9)	0.0054 (9)	−0.0015 (9)
C7	0.0169 (10)	0.0248 (12)	0.0232 (11)	0.0006 (9)	0.0021 (9)	0.0037 (9)
C8	0.0163 (10)	0.0250 (11)	0.0257 (11)	−0.0027 (9)	0.0035 (9)	−0.0019 (10)
C9	0.0168 (10)	0.0214 (12)	0.0264 (11)	−0.0005 (8)	0.0073 (9)	0.0014 (9)
C10	0.0180 (10)	0.0284 (12)	0.0256 (11)	0.0011 (9)	0.0105 (9)	−0.0028 (9)
C11	0.0229 (11)	0.0277 (12)	0.0229 (11)	−0.0014 (9)	0.0121 (9)	−0.0053 (9)
C11A	0.0168 (10)	0.0255 (12)	0.0164 (10)	−0.0046 (8)	0.0048 (8)	−0.0034 (9)

Geometric parameters (Å, º) top

Se1—C11A	1.847 (2)	C6—H6B	0.9900
Se1—N2	1.875 (2)	C7—C8	1.527 (3)
N2—N3	1.274 (3)	C7—H7A	0.9900
N3—C3A	1.377 (3)	C7—H7B	0.9900
C3A—C11A	1.370 (3)	C8—C9	1.536 (3)
C3A—C4	1.503 (3)	C8—H8A	0.9900
C4—C5	1.538 (3)	C8—H8B	0.9900
C4—H4A	0.9900	C9—C10	1.500 (3)
C4—H4B	0.9900	C9—H9A	0.9900
C5—C6	1.531 (3)	C9—H9B	0.9900
C5—H5A	0.9900	C10—C11	1.327 (3)
C5—H5B	0.9900	C10—H10	0.9500
C6—C7	1.529 (3)	C11—C11A	1.475 (3)
C6—H6A	0.9900	C11—H11	0.9500

C11A—Se1—N2	87.18 (9)	C6—C7—H7A	108.8
N3—N2—Se1	110.36 (16)	C8—C7—H7B	108.8
N2—N3—C3A	118.2 (2)	C6—C7—H7B	108.8
C11A—C3A—N3	115.3 (2)	H7A—C7—H7B	107.6
C11A—C3A—C4	126.8 (2)	C7—C8—C9	113.71 (19)
N3—C3A—C4	117.9 (2)	C7—C8—H8A	108.8
C3A—C4—C5	112.50 (19)	C9—C8—H8A	108.8
C3A—C4—H4A	109.1	C7—C8—H8B	108.8
C5—C4—H4A	109.1	C9—C8—H8B	108.8
C3A—C4—H4B	109.1	H8A—C8—H8B	107.7
C5—C4—H4B	109.1	C10—C9—C8	112.46 (19)
H4A—C4—H4B	107.8	C10—C9—H9A	109.1
C6—C5—C4	113.46 (19)	C8—C9—H9A	109.1
C6—C5—H5A	108.9	C10—C9—H9B	109.1
C4—C5—H5A	108.9	C8—C9—H9B	109.1
C6—C5—H5B	108.9	H9A—C9—H9B	107.8
C4—C5—H5B	108.9	C11—C10—C9	126.8 (2)
H5A—C5—H5B	107.7	C11—C10—H10	116.6
C7—C6—C5	114.7 (2)	C9—C10—H10	116.6
C7—C6—H6A	108.6	C10—C11—C11A	124.5 (2)
C5—C6—H6A	108.6	C10—C11—H11	117.8
C7—C6—H6B	108.6	C11A—C11—H11	117.8
C5—C6—H6B	108.6	C3A—C11A—C11	127.3 (2)
H6A—C6—H6B	107.6	C3A—C11A—Se1	109.01 (17)
C8—C7—C6	114.0 (2)	C11—C11A—Se1	123.72 (17)
C8—C7—H7A	108.8

C11A—Se1—N2—N3	−0.04 (18)	C8—C9—C10—C11	110.4 (3)
Se1—N2—N3—C3A	0.2 (3)	C9—C10—C11—C11A	0.2 (4)
N2—N3—C3A—C11A	−0.3 (3)	N3—C3A—C11A—C11	−178.8 (2)
N2—N3—C3A—C4	178.1 (2)	C4—C3A—C11A—C11	2.9 (4)
C11A—C3A—C4—C5	108.5 (3)	N3—C3A—C11A—Se1	0.3 (3)
N3—C3A—C4—C5	−69.7 (3)	C4—C3A—C11A—Se1	−178.00 (18)
C3A—C4—C5—C6	−56.7 (3)	C10—C11—C11A—C3A	−92.0 (3)
C4—C5—C6—C7	−63.5 (3)	C10—C11—C11A—Se1	89.0 (3)
C5—C6—C7—C8	149.2 (2)	N2—Se1—C11A—C3A	−0.12 (17)
C6—C7—C8—C9	−65.1 (3)	N2—Se1—C11A—C11	179.0 (2)
C7—C8—C9—C10	−57.5 (3)

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