N-[(1Z)-Cyclo­dec-5-yn-1-yl­idene]hydroxyl­amine

Detert, H.; Schollmeyer, D.

doi:10.1107/S2414314625004146

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 5| May 2025| x250414

https://doi.org/10.1107/S2414314625004146

Open

access

N-[(1Z)-Cyclodec-5-yn-1-ylidene]hydroxylamine

Heiner Detert ^a ^* and Dieter Schollmeyer ^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 5 May 2025; accepted 7 May 2025; online 13 May 2025)

The crystal structure of cyclodecynone oxime, C₁₀H₁₅NO, is reported. Two twist-boat-shaped cycloalkynes are centrosymmetrically connected via oxime hydrogen bridges. Deformation of the alkyne unit results from ring strain.

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

CCDC reference: 2449294

Structure description

The title compound, C₁₀H₁₅NO (Fig. 1), was prepared as part of a project focusing on medium-sized rings and transannular reactions. Whereas the bond angle of 119.76 (9)° at the carbonyl group (C2—C1—C10) is perfect for a sp²-hybridized carbon, the C—C—C bond angles on the methylene tether are significantly larger than for an ideal sp³ hybridization. Except for the propargylic carbon atoms C4—C5—C6: 111.67 (9)°, C7—C8—C9: 112.64 (9)°, the C—C—C bond angles vary between 114.75 (10)° and 116.98 (9)°. Ring strain also distorts the alkyne unit, bond angles on the acetylenic carbons are reduced to 172.02 (11)° for C5—C6—C7 and to 172.38 (11)° for C6—C7—C8. The cyclodecyne ring adopts a twist-boat conformation with C4 and C9 being fore and aft. The other atoms are mostly coplanar, only C1 lies 0.477 (1) Å above and C2 lies −0.5213 (11) Å below this plane. The oxime unit (C1, N11, O12, H122) is planar with an r.m.s. deviation of 0.022 Å. Centrosymmetric dimers are formed via hydrogen bridging. The oxime units form a planar six-membered ring via two hydrogen bridges O12—H122—N11ⁱ, H122⋯N11ⁱ: 1.908 (19) Å (symmetry code as in Table 1) This gives the dimer the shape of two steps in a staircase (Fig. 2), the angle between the cyclodecyne planes and the di-oxime plane being 75.1 (5)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H122⋯N11ⁱ	0.971 (19)	1.908 (19)	2.8030 (12)	151.9 (16)
Symmetry code: (i) .

Figure 1
Perspective view (Spek, 2009

) of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
Part of the packing diagram. View along b-axis direction (Spek, 2009

Synthesis and crystallization

Synthetic and spectroscopic details:

The title compound was prepared by G. Krämer (Krämer, 1996 ; Krämer et al., 2009 ). Oxidation of decaline to the hydroperoxide, rearrangement to hydroxyketone/hemiacetal and conversion via semicarbazone to 1,2,3-selenadiazole (Detert et al., 1992 ), oxidation and pyrolysis yielded cyclodecynone (Gleiter et al., 1988 ). The oxime was formed according to Hanack (Hanack et al., 1972 ).

The annotation of the NMR signals follows IUPAC nomenclature. ¹H-NMR (200 MHz, CDCl₃): 9.1 (bs, 1 H, OH), 2.75 (t, 2 H, J = 6.1 Hz), 2.37 (t, 2 H, J = 6 Hz), 2.20-1.95 (m, 6 H, 3,4,7-H), 1.80 (m, 4 H, 8,9-H); ¹³C-NMR (100 MHz, CDCl₃): 160.3 (C=N), 84.9, 83.4 (C-5, C-6), 33.5, 30.6, 26.1, 24.3, 23.9, 19.7, 18.3.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₁₅NO
M_r	165.23
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	120
a, b, c (Å)	9.5469 (4), 8.9830 (3), 21.8191 (7)
V (Å³)	1871.20 (12)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.80 × 0.48 × 0.14

Data collection
Diffractometer	Stoe IPDS 2T
No. of measured, independent and observed [I > 2σ(I)] reflections	6155, 2574, 2225
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.691

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.111, 1.04
No. of reflections	2574
No. of parameters	162
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.17
Computer programs: X-AREA WinXpose, Recipe and Integrate (Stoe & Cie, 2020 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 2449294

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314625004146/bt4170sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625004146/bt4170Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314625004146/bt4170Isup3.cml

checkCIF report

Computing details top

N-[(1Z)-Cyclodec-5-yn-1-ylidene]hydroxylamine top

Crystal data top

C₁₀H₁₅NO	D_x = 1.173 Mg m⁻³
M_r = 165.23	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9411 reflections
a = 9.5469 (4) Å	θ = 2.8–29.9°
b = 8.9830 (3) Å	µ = 0.08 mm⁻¹
c = 21.8191 (7) Å	T = 120 K
V = 1871.20 (12) Å³	Plate, colorless
Z = 8	0.80 × 0.48 × 0.14 mm
F(000) = 720

Data collection top

Stoe IPDS 2T diffractometer	2225 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12x0.4mm long-fine focus	R_int = 0.023
Detector resolution: 6.67 pixels mm^-1	θ_max = 29.4°, θ_min = 2.8°
rotation method, ω scans	h = −11→13
6155 measured reflections	k = −12→10
2574 independent reflections	l = −30→25

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	All H-atom parameters refined
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0486P)² + 0.7721P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2574 reflections	Δρ_max = 0.37 e Å⁻³
162 parameters	Δρ_min = −0.17 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. All hydrogen atoms were located in a difference map. The H atom bonded to O was freely refined. The coordinates of the H atoms attached to carbon atoms were freely refined. Their displacement parameters were also refined constraining the U values of each pair of H atoms bonded to the same C atom to be equal.

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

	x	y	z	U_iso*/U_eq
C1	0.58239 (10)	0.31386 (12)	0.09451 (4)	0.0202 (2)
C2	0.53594 (12)	0.15439 (12)	0.08775 (5)	0.0239 (2)
H2A	0.5224 (16)	0.1130 (17)	0.1307 (7)	0.035 (3)*
H2B	0.6203 (17)	0.0993 (17)	0.0708 (7)	0.035 (3)*
C3	0.40563 (12)	0.12659 (12)	0.04840 (5)	0.0265 (2)
H3A	0.4264 (15)	0.1549 (17)	0.0047 (7)	0.034 (3)*
H3B	0.3876 (16)	0.0187 (17)	0.0483 (7)	0.034 (3)*
C4	0.27114 (12)	0.20571 (13)	0.06758 (5)	0.0269 (2)
H4A	0.1977 (16)	0.1686 (17)	0.0414 (7)	0.034 (3)*
H4B	0.2806 (16)	0.3164 (18)	0.0633 (7)	0.034 (3)*
C5	0.22458 (13)	0.17707 (15)	0.13387 (6)	0.0312 (3)
H5A	0.1284 (18)	0.2109 (19)	0.1418 (8)	0.044 (3)*
H5B	0.2294 (18)	0.072 (2)	0.1442 (7)	0.044 (3)*
C6	0.31476 (12)	0.25459 (12)	0.17804 (5)	0.0253 (2)
C7	0.39879 (12)	0.32077 (13)	0.20810 (5)	0.0253 (2)
C8	0.51520 (14)	0.39742 (16)	0.23847 (5)	0.0337 (3)
H8A	0.5657 (18)	0.3253 (19)	0.2646 (8)	0.046 (3)*
H8B	0.4801 (19)	0.4749 (19)	0.2667 (8)	0.046 (3)*
C9	0.61843 (12)	0.46629 (14)	0.19295 (5)	0.0280 (2)
H9A	0.6953 (15)	0.5097 (16)	0.2174 (7)	0.031 (3)*
H9B	0.5754 (15)	0.5494 (16)	0.1713 (7)	0.031 (3)*
C10	0.67983 (11)	0.35670 (13)	0.14614 (5)	0.0249 (2)
H10A	0.7644 (16)	0.4019 (17)	0.1266 (6)	0.033 (3)*
H10B	0.7124 (15)	0.2666 (17)	0.1673 (7)	0.033 (3)*
N11	0.54369 (9)	0.40276 (10)	0.05199 (4)	0.02058 (19)
O12	0.60094 (8)	0.54785 (9)	0.05794 (4)	0.02628 (19)
H122	0.5675 (19)	0.595 (2)	0.0207 (9)	0.054 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0171 (4)	0.0245 (5)	0.0190 (4)	0.0022 (4)	0.0032 (3)	0.0029 (4)
C2	0.0263 (5)	0.0209 (5)	0.0247 (5)	0.0050 (4)	0.0043 (4)	0.0016 (4)
C3	0.0315 (6)	0.0224 (5)	0.0256 (5)	−0.0018 (4)	0.0027 (4)	−0.0059 (4)
C4	0.0238 (5)	0.0308 (6)	0.0262 (5)	−0.0040 (4)	−0.0017 (4)	−0.0060 (4)
C5	0.0279 (6)	0.0333 (6)	0.0324 (6)	−0.0104 (5)	0.0077 (5)	−0.0064 (5)
C6	0.0275 (5)	0.0268 (5)	0.0214 (5)	−0.0009 (4)	0.0082 (4)	0.0014 (4)
C7	0.0276 (5)	0.0311 (5)	0.0170 (4)	0.0023 (4)	0.0035 (4)	0.0018 (4)
C8	0.0328 (6)	0.0496 (7)	0.0186 (5)	−0.0020 (6)	−0.0046 (4)	−0.0022 (5)
C9	0.0273 (5)	0.0317 (6)	0.0251 (5)	−0.0036 (5)	−0.0084 (4)	0.0012 (4)
C10	0.0192 (5)	0.0302 (5)	0.0254 (5)	−0.0002 (4)	−0.0048 (4)	0.0077 (4)
N11	0.0209 (4)	0.0218 (4)	0.0190 (4)	−0.0011 (3)	0.0023 (3)	0.0027 (3)
O12	0.0287 (4)	0.0248 (4)	0.0253 (4)	−0.0075 (3)	−0.0046 (3)	0.0079 (3)

Geometric parameters (Å, º) top

C1—N11	1.2785 (13)	C5—H5B	0.969 (18)
C1—C2	1.5069 (15)	C6—C7	1.1946 (16)
C1—C10	1.5108 (14)	C7—C8	1.4656 (16)
C2—C3	1.5319 (16)	C8—C9	1.5298 (17)
C2—H2A	1.017 (15)	C8—H8A	0.989 (17)
C2—H2B	1.015 (16)	C8—H8B	0.988 (17)
C3—C4	1.5260 (16)	C9—C10	1.5349 (17)
C3—H3A	1.007 (15)	C9—H9A	0.987 (15)
C3—H3B	0.984 (15)	C9—H9B	0.974 (15)
C4—C5	1.5349 (16)	C10—H10A	0.999 (15)
C4—H4A	0.964 (15)	C10—H10B	0.983 (15)
C4—H4B	1.003 (16)	N11—O12	1.4193 (11)
C5—C6	1.4680 (16)	O12—H122	0.971 (19)
C5—H5A	0.983 (17)

N11—C1—C2	115.96 (9)	C4—C5—H5B	111.6 (10)
N11—C1—C10	124.04 (10)	H5A—C5—H5B	107.7 (14)
C2—C1—C10	119.76 (9)	C7—C6—C5	172.02 (11)
C1—C2—C3	116.67 (9)	C6—C7—C8	172.38 (11)
C1—C2—H2A	107.1 (9)	C7—C8—C9	112.64 (9)
C3—C2—H2A	110.7 (9)	C7—C8—H8A	108.8 (10)
C1—C2—H2B	105.4 (9)	C9—C8—H8A	109.0 (10)
C3—C2—H2B	111.2 (9)	C7—C8—H8B	110.8 (10)
H2A—C2—H2B	104.9 (12)	C9—C8—H8B	109.8 (10)
C4—C3—C2	116.98 (9)	H8A—C8—H8B	105.5 (14)
C4—C3—H3A	107.9 (9)	C8—C9—C10	114.75 (10)
C2—C3—H3A	109.3 (9)	C8—C9—H9A	106.7 (9)
C4—C3—H3B	108.2 (9)	C10—C9—H9A	109.2 (9)
C2—C3—H3B	107.7 (9)	C8—C9—H9B	110.6 (9)
H3A—C3—H3B	106.3 (12)	C10—C9—H9B	109.3 (9)
C3—C4—C5	115.09 (10)	H9A—C9—H9B	105.8 (12)
C3—C4—H4A	106.8 (9)	C1—C10—C9	115.11 (9)
C5—C4—H4A	106.8 (9)	C1—C10—H10A	106.5 (8)
C3—C4—H4B	111.1 (9)	C9—C10—H10A	109.4 (9)
C5—C4—H4B	106.3 (8)	C1—C10—H10B	109.6 (9)
H4A—C4—H4B	110.6 (12)	C9—C10—H10B	109.6 (9)
C6—C5—C4	111.67 (9)	H10A—C10—H10B	106.3 (12)
C6—C5—H5A	106.6 (10)	C1—N11—O12	113.33 (8)
C4—C5—H5A	112.7 (10)	N11—O12—H122	101.5 (11)
C6—C5—H5B	106.3 (10)

N11—C1—C2—C3	−23.67 (13)	N11—C1—C10—C9	69.25 (13)
C10—C1—C2—C3	161.71 (9)	C2—C1—C10—C9	−116.59 (11)
C1—C2—C3—C4	−57.70 (13)	C8—C9—C10—C1	76.41 (12)
C2—C3—C4—C5	−55.44 (14)	C2—C1—N11—O12	−174.64 (8)
C3—C4—C5—C6	72.79 (13)	C10—C1—N11—O12	−0.28 (14)
C7—C8—C9—C10	−55.59 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H122···N11ⁱ	0.971 (19)	1.908 (19)	2.8030 (12)	151.9 (16)

Symmetry code: (i) −x+1, −y+1, −z.

References

Detert, H., Antony–Mayer, C. & Meier, H. (1992). Angew. Chem. 104, 755–757. CrossRef CAS Google Scholar
Gleiter, R., Kratz, D. & Schehlmann, V. (1988). Tetrahedron Lett. 29, 2813–2816. CrossRef Google Scholar
Hanack, M., Harding, C. E. & Derocque, J.-L. (1972). Chem. Ber. 105, 421–433. CrossRef Google Scholar
Krämer, G. (1996). PhD Thesis, University of Mainz, p. 119. Google Scholar
Meier, H., Krämer, G. & Detert, H. (2009). Heterocycles 78, 2201–2208. CrossRef Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2020). X-RED and X-AREA. Stoe & Cie, Darmstadt, Germany. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.