N,N-Di­cyclo­hexyl­nitramine

Gajda, K.; Dziuk, B.; Daszkiewicz, Z.; Zarychta, B.

doi:10.1107/S2414314616015133

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161513

doi:10.1107/S2414314616015133

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N,N-Dicyclohexylnitramine

Katarzyna Gajda,^a ^* Błażej Dziuk,^a Zdzisław Daszkiewicz ^a and Bartosz Zarychta ^a

^aFaculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
^*Correspondence e-mail: katarzyna.gajda@uni.opole.pl

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 8 September 2016; accepted 26 September 2016; online 30 September 2016)

Molecules of the title compound, C₁₂H₂₂N₂O₂, are composed of an nitramine group substituted by two cyclohexane rings. The cyclohexane rings have chair conformations, with the exocyclic C—N bonds in axial orientations. In the crystal, C—H⋯O hydrogen bonds connect the molecules into C(6) [-101] zigzag chains.

Keywords: crystal structure; nitramines; hydrogen bonds.

CCDC reference: 1506353

Structure description

The study of the chemistry of aliphatic nitrosoamines began in 1863 when Geuther obtained N-nitrosodiethylamine by the reaction of diethylamine hydrochloride with sodium nitrite (Taylor & Price, 1929 ). Many nitrosamines showed carcinogenic properties for animals but it is difficult to determine these properties for humans because of the very low typical absorption. For this reason, determination of the danger for humans is very complicated (Crosby & Sawyer, 1976 ).

The amide group is substituted by two cyclohexane rings (Fig. 1). The N1—N2 bond length is notably shorter [1.3509 (13) Å] than the distance characteristic of an N—N single bond (1.42 Å) but longer than the distance of an N=N double bond (1.24 Å), indicating partial double-bond character. The geometry of the nitramine group is typical, and corresponds well with similar compounds (Prezhdo et al., 2001b ; Zarychta et al., 2005a ,b , 2011 ). Both cyclohexane rings have chair conformations with the exocyclic C—N bonds in axial orientations.

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

The crystal structure features weak C—H⋯O interactions, which connect the molecules into [ $[\overline{1}]$ 01] C₁¹(6) zigzag chains (Table 1). The packing is shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O2ⁱ	0.97	2.60	3.5684 (14)	176
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
The crystal packing of the title compound, viewed along the a axis.

Synthesis and crystallization

N,N-dimethylnitramine was prepared as follows (Prezhdo et al., 2001a ). To a solution of 1.05 g of N-nitrosodicyclohexylamine in 50 ml of acetone was added 25 ml of a buffer solution containing 6 g of K₂HPO₄ and 0.7 g of KH₂PO₄ and then, in four portions over a period of 4 h, 3 g of oxone (2KHSO₅·KHSO₄·K₂SO₄) and stirred for the next 3 h. The product was extracted with methylene chloride (4 × 25 ml). The extract was dried over anhydrous magnesium sulfate, the solvent was evaporated, and the residue was recrystallized from iso-octane solution. Yield = 0.8 g, m.p. 137–138°C.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₂₂N₂O₂
M_r	226.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	5.9136 (1), 19.1658 (4), 10.8946 (2)
β (°)	91.852 (2)
V (Å³)	1234.14 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.04 × 0.04 × 0.03

Data collection
Diffractometer	Oxford Diffraction Xcalibur CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8287, 2425, 1892
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.084, 1.07
No. of reflections	2425
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.15
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXS2014 and SHELXTL (Sheldrick, 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Structural data

CCDC reference: 1506353

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2414314616015133/hb4079sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616015133/hb4079Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616015133/hb4079Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis CCD (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

N-Cyclohexyl-N-nitrocyclohexanamine top

Crystal data top

C₁₂H₂₂N₂O₂	F(000) = 496
M_r = 226.31	D_x = 1.218 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.9136 (1) Å	Cell parameters from 8287 reflections
b = 19.1658 (4) Å	θ = 3.6–26.0°
c = 10.8946 (2) Å	µ = 0.08 mm⁻¹
β = 91.852 (2)°	T = 100 K
V = 1234.14 (4) Å³	Plate, colourless
Z = 4	0.04 × 0.04 × 0.03 mm

Data collection top

Oxford Diffraction Xcalibur CCD diffractometer	1892 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θ_max = 26.0°, θ_min = 3.6°
ω–scan	h = −7→7
8287 measured reflections	k = −23→23
2425 independent reflections	l = −13→10

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0401P)² + 0.1204P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2425 reflections	Δρ_max = 0.18 e Å⁻³
145 parameters	Δρ_min = −0.15 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.

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

	x	y	z	U_iso*/U_eq
O1	0.72029 (16)	0.12483 (4)	0.64176 (8)	0.0372 (2)
O2	0.64140 (15)	0.23560 (5)	0.64377 (8)	0.0380 (2)
N1	0.83491 (16)	0.19259 (5)	0.49004 (9)	0.0257 (2)
N2	0.72928 (17)	0.18401 (5)	0.59711 (9)	0.0269 (2)
C1	0.94810 (19)	0.13124 (6)	0.43775 (10)	0.0229 (3)
H1A	0.8895	0.0901	0.4795	0.027*
C2	0.8906 (2)	0.12227 (6)	0.30137 (11)	0.0272 (3)
H2A	0.9519	0.1609	0.2556	0.033*
H2B	0.7277	0.1218	0.2877	0.033*
C3	0.9913 (2)	0.05376 (6)	0.25735 (12)	0.0332 (3)
H3A	0.9191	0.0151	0.2982	0.040*
H3B	0.9610	0.0489	0.1697	0.040*
C4	1.2452 (2)	0.05060 (7)	0.28348 (12)	0.0334 (3)
H4A	1.3010	0.0050	0.2606	0.040*
H4B	1.3194	0.0852	0.2337	0.040*
C5	1.3044 (2)	0.06395 (6)	0.41772 (12)	0.0324 (3)
H5A	1.4677	0.0657	0.4293	0.039*
H5B	1.2488	0.0257	0.4665	0.039*
C6	1.20285 (19)	0.13213 (6)	0.46228 (11)	0.0267 (3)
H6A	1.2356	0.1377	0.5495	0.032*
H6B	1.2693	0.1711	0.4197	0.032*
C7	0.87648 (19)	0.26368 (6)	0.44305 (11)	0.0238 (3)
H7A	0.9683	0.2572	0.3706	0.029*
C8	0.6611 (2)	0.30047 (6)	0.39599 (12)	0.0295 (3)
H8A	0.5820	0.2711	0.3361	0.035*
H8B	0.5617	0.3084	0.4637	0.035*
C9	0.7201 (2)	0.36990 (6)	0.33712 (12)	0.0316 (3)
H9A	0.8051	0.3614	0.2639	0.038*
H9B	0.5817	0.3940	0.3125	0.038*
C10	0.8586 (2)	0.41578 (6)	0.42459 (12)	0.0325 (3)
H10A	0.7687	0.4280	0.4943	0.039*
H10B	0.8988	0.4586	0.3831	0.039*
C11	1.0727 (2)	0.37853 (6)	0.46953 (12)	0.0319 (3)
H11A	1.1548	0.4081	0.5279	0.038*
H11B	1.1691	0.3703	0.4006	0.038*
C12	1.0191 (2)	0.30900 (6)	0.53055 (11)	0.0281 (3)
H12A	1.1588	0.2850	0.5529	0.034*
H12B	0.9374	0.3173	0.6049	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0500 (6)	0.0309 (5)	0.0315 (5)	0.0028 (4)	0.0135 (4)	0.0110 (4)
O2	0.0488 (6)	0.0336 (5)	0.0326 (5)	0.0083 (4)	0.0195 (4)	−0.0017 (4)
N1	0.0321 (6)	0.0234 (5)	0.0221 (5)	0.0019 (4)	0.0107 (4)	0.0028 (4)
N2	0.0291 (5)	0.0294 (6)	0.0224 (5)	0.0017 (4)	0.0055 (4)	0.0030 (4)
C1	0.0263 (6)	0.0199 (6)	0.0227 (6)	0.0002 (5)	0.0038 (5)	0.0010 (5)
C2	0.0249 (6)	0.0288 (7)	0.0277 (6)	−0.0029 (5)	−0.0031 (5)	−0.0019 (5)
C3	0.0415 (8)	0.0301 (7)	0.0283 (7)	−0.0070 (6)	0.0042 (6)	−0.0075 (5)
C4	0.0401 (7)	0.0249 (7)	0.0359 (7)	0.0043 (6)	0.0120 (6)	−0.0001 (5)
C5	0.0280 (7)	0.0325 (7)	0.0370 (7)	0.0061 (5)	0.0040 (5)	0.0077 (6)
C6	0.0277 (7)	0.0289 (6)	0.0232 (6)	0.0001 (5)	−0.0034 (5)	0.0019 (5)
C7	0.0283 (6)	0.0208 (6)	0.0227 (6)	0.0008 (5)	0.0055 (5)	0.0015 (5)
C8	0.0273 (6)	0.0295 (7)	0.0315 (7)	0.0001 (5)	−0.0007 (5)	0.0029 (5)
C9	0.0317 (7)	0.0322 (7)	0.0308 (7)	0.0048 (5)	0.0007 (5)	0.0082 (5)
C10	0.0393 (7)	0.0235 (6)	0.0351 (7)	0.0029 (6)	0.0065 (6)	0.0018 (5)
C11	0.0322 (7)	0.0290 (7)	0.0345 (7)	−0.0045 (5)	−0.0006 (5)	−0.0023 (5)
C12	0.0308 (6)	0.0260 (6)	0.0274 (6)	0.0037 (5)	−0.0016 (5)	−0.0014 (5)

Geometric parameters (Å, º) top

O1—N2	1.2360 (12)	C6—H6A	0.9700
O2—N2	1.2342 (12)	C6—H6B	0.9700
N1—N2	1.3509 (13)	C7—C12	1.5238 (16)
N1—C1	1.4764 (14)	C7—C8	1.5297 (16)
N1—C7	1.4789 (14)	C7—H7A	0.9800
C1—C6	1.5216 (16)	C8—C9	1.5225 (16)
C1—C2	1.5231 (16)	C8—H8A	0.9700
C1—H1A	0.9800	C8—H8B	0.9700
C2—C3	1.5255 (17)	C9—C10	1.5172 (18)
C2—H2A	0.9700	C9—H9A	0.9700
C2—H2B	0.9700	C9—H9B	0.9700
C3—C4	1.5202 (18)	C10—C11	1.5206 (18)
C3—H3A	0.9700	C10—H10A	0.9700
C3—H3B	0.9700	C10—H10B	0.9700
C4—C5	1.5145 (18)	C11—C12	1.5271 (17)
C4—H4A	0.9700	C11—H11A	0.9700
C4—H4B	0.9700	C11—H11B	0.9700
C5—C6	1.5240 (16)	C12—H12A	0.9700
C5—H5A	0.9700	C12—H12B	0.9700
C5—H5B	0.9700

N2—N1—C1	117.66 (9)	C1—C6—H6B	109.8
N2—N1—C7	119.84 (9)	C5—C6—H6B	109.8
C1—N1—C7	121.18 (9)	H6A—C6—H6B	108.2
O2—N2—O1	123.29 (9)	N1—C7—C12	113.79 (9)
O2—N2—N1	118.09 (9)	N1—C7—C8	113.25 (9)
O1—N2—N1	118.59 (9)	C12—C7—C8	112.64 (10)
N1—C1—C6	112.45 (9)	N1—C7—H7A	105.4
N1—C1—C2	112.12 (9)	C12—C7—H7A	105.4
C6—C1—C2	111.17 (9)	C8—C7—H7A	105.4
N1—C1—H1A	106.9	C9—C8—C7	110.15 (10)
C6—C1—H1A	106.9	C9—C8—H8A	109.6
C2—C1—H1A	106.9	C7—C8—H8A	109.6
C1—C2—C3	109.07 (10)	C9—C8—H8B	109.6
C1—C2—H2A	109.9	C7—C8—H8B	109.6
C3—C2—H2A	109.9	H8A—C8—H8B	108.1
C1—C2—H2B	109.9	C10—C9—C8	111.61 (10)
C3—C2—H2B	109.9	C10—C9—H9A	109.3
H2A—C2—H2B	108.3	C8—C9—H9A	109.3
C4—C3—C2	111.63 (10)	C10—C9—H9B	109.3
C4—C3—H3A	109.3	C8—C9—H9B	109.3
C2—C3—H3A	109.3	H9A—C9—H9B	108.0
C4—C3—H3B	109.3	C9—C10—C11	110.93 (10)
C2—C3—H3B	109.3	C9—C10—H10A	109.5
H3A—C3—H3B	108.0	C11—C10—H10A	109.5
C5—C4—C3	111.73 (10)	C9—C10—H10B	109.5
C5—C4—H4A	109.3	C11—C10—H10B	109.5
C3—C4—H4A	109.3	H10A—C10—H10B	108.0
C5—C4—H4B	109.3	C10—C11—C12	111.54 (10)
C3—C4—H4B	109.3	C10—C11—H11A	109.3
H4A—C4—H4B	107.9	C12—C11—H11A	109.3
C4—C5—C6	111.79 (10)	C10—C11—H11B	109.3
C4—C5—H5A	109.3	C12—C11—H11B	109.3
C6—C5—H5A	109.3	H11A—C11—H11B	108.0
C4—C5—H5B	109.3	C7—C12—C11	110.10 (10)
C6—C5—H5B	109.3	C7—C12—H12A	109.6
H5A—C5—H5B	107.9	C11—C12—H12A	109.6
C1—C6—C5	109.42 (10)	C7—C12—H12B	109.6
C1—C6—H6A	109.8	C11—C12—H12B	109.6
C5—C6—H6A	109.8	H12A—C12—H12B	108.2

C1—N1—N2—O2	177.38 (10)	C2—C1—C6—C5	−59.24 (12)
C7—N1—N2—O2	10.30 (16)	C4—C5—C6—C1	55.84 (13)
C1—N1—N2—O1	−4.46 (15)	N2—N1—C7—C12	58.93 (14)
C7—N1—N2—O1	−171.54 (10)	C1—N1—C7—C12	−107.69 (12)
N2—N1—C1—C6	−100.93 (12)	N2—N1—C7—C8	−71.41 (13)
C7—N1—C1—C6	65.97 (13)	C1—N1—C7—C8	121.98 (11)
N2—N1—C1—C2	132.93 (11)	N1—C7—C8—C9	−174.08 (9)
C7—N1—C1—C2	−60.17 (13)	C12—C7—C8—C9	55.01 (13)
N1—C1—C2—C3	−173.68 (9)	C7—C8—C9—C10	−55.28 (13)
C6—C1—C2—C3	59.49 (12)	C8—C9—C10—C11	56.61 (14)
C1—C2—C3—C4	−56.37 (13)	C9—C10—C11—C12	−56.53 (14)
C2—C3—C4—C5	54.20 (14)	N1—C7—C12—C11	174.42 (9)
C3—C4—C5—C6	−53.84 (14)	C8—C7—C12—C11	−54.94 (13)
N1—C1—C6—C5	174.10 (9)	C10—C11—C12—C7	55.23 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O2ⁱ	0.97	2.60	3.5684 (14)	176

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

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