2,6,6-Trimethyl­cyclo­hexene-1-carbaldehyde oxime

Parthasarathy, R.; Jenniefer, S.J.; Muthiah, P.T.; Sulochana, N.

doi:10.1107/S1600536811037895

organic compounds

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Volume 67| Part 10| October 2011| Page o2732

https://doi.org/10.1107/S1600536811037895

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2,6,6-Trimethylcyclohexene-1-carbaldehyde oxime

Rajasekaran Parthasarathy,^a Samson Jegan Jenniefer,^b Packianathan Thomas Muthiah ^b ^* and Nagarajan Sulochana ^c

^aDepartment of Chemistry, National Institute of Technology, Tiruchirappalli 620 015, India, ^bSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu, India, and ^cDepartment of Chemistry, National Institute of Technology, Karaikal 609 605, India
^*Correspondence e-mail: tommtrichy@yahoo.co.in

(Received 6 September 2011; accepted 16 September 2011; online 30 September 2011)

In the crystal of the title compound C₁₀H₁₇NO, synthesized by the reaction of β-cyclocitral with hydroxylamine hydrochloride, inversion-related molecules are linked by a pair of O—H⋯N hydrogen-bonding interactions between the oxime functionalities, forming R₂²(6) loops. The molecular conformation is stabilized by intramolecular methyl C—H⋯N interactions. The cyclohexene ring has the typical half-chair conformation.

Related literature

For applications of oximes in organic syntheses, see: Cerny et al. (1969 ); Donaruma & Heldt (1960 ); Kutney et al. (1992 ); Touster (1953 ). For graph-set notation, see: Etter et al. (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₀H₁₇NO
M_r = 167.25
Triclinic, $[P \overline 1]$
a = 7.5670 (3) Å
b = 7.7208 (3) Å
c = 9.3072 (4) Å
α = 81.212 (3)°
β = 76.590 (3)°
γ = 71.385 (3)°
V = 499.43 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 296 K
0.09 × 0.06 × 0.05 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.994, T_max = 0.997
13971 measured reflections
3341 independent reflections
2134 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.191
S = 1.06
3341 reflections
118 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.86 (3)	2.02 (3)	2.8346 (18)	158 (2)
C9—H9A⋯N1	0.96	2.57	3.1979 (19)	123
C10—H10A⋯N1	0.96	2.43	3.0762 (17)	125
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811037895/zs2144sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811037895/zs2144Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811037895/zs2144Isup3.cml

checkCIF report

Comment top

An oxime is an important functional group in organic chemistry because it is not only used as an efficient protecting group for carbonyls but also may be used for the purification of carbonyl compounds (Donaruma & Heldt, 1960). Moreover oximes are used for the preparation of many compounds such as amines by reduction (Cerny et al., 1969), nitro compounds by oxidation, amides by the Beckmann rearrangement and carbonyl compounds from non carbonyl compounds (Touster, 1953). The title compound C₁₀H₁₇NO is a key intermediate in the synthesis of aroma compounds such as β-cyclogeranyl nitrile which can be used for the synthesis of the important aroma compound β-damascone (Kutney et al., 1992). Herein, we report the crystal structure of the title compound (Fig. 1) in which each molecule is connected to an inversion-related molecule through O—H···N hydrogen bonds, (Table 1) forming a cyclic dimer [graph-set R²₂(6) (Etter et al., 1990; Bernstein et al., 1995] (Fig. 2). These cyclic DA—AD (Donor Acceptor–Acceptor Donor) interactions involving pairs of O—H···N hydrogen bonds between the oxime functionalities are similar to the O—H···O interactions observed in carboxylic acid dimers. The crystal structure is stabilized by intramolecular methyl C—H···N_oxime hydrogen-bonding interactions.

Related literature top

For applications of oximes in organic syntheses, see: Cerny et al. (1969); Donaruma & Heldt (1960); Kutney et al. (1992); Touster (1953). For graph-set notation, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

To a mixture of 4.6 g (0.065 mol) of hydroxylamine hydrochloride in 50 ml of H₂O and 10 g (0.065 mol) of β-cyclocitral, a solution of 3.5 g (0.033 mol) of sodium carbonate in 15 ml of H₂O was added dropwise. The mixture was stirred at room temperature for ten minutes and the solid product which formed was collected and recrystallized from hexane.

Structure description top

For applications of oximes in organic syntheses, see: Cerny et al. (1969); Donaruma & Heldt (1960); Kutney et al. (1992); Touster (1953). For graph-set notation, see: Etter et al. (1990); Bernstein et al. (1995).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The centrosymmetric R²₂(6) hydrogen-bonded dimer units, with hydrogen bonds shown as dashed lines. For symmetry code (i), see Table 1.

2,6,6-Trimethylcyclohexene-1-carbaldehyde oxime top

Crystal data top

C₁₀H₁₇NO	Z = 2
M_r = 167.25	F(000) = 184
Triclinic, P1	D_x = 1.112 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5670 (3) Å	Cell parameters from 3341 reflections
b = 7.7208 (3) Å	θ = 2.3–33.0°
c = 9.3072 (4) Å	µ = 0.07 mm⁻¹
α = 81.212 (3)°	T = 296 K
β = 76.590 (3)°	Prism, colourless
γ = 71.385 (3)°	0.09 × 0.06 × 0.05 mm
V = 499.43 (4) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3341 independent reflections
Radiation source: fine-focus sealed tube	2134 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 33.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
T_min = 0.994, T_max = 0.997	k = −11→11
13971 measured reflections	l = −12→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0999P)² + 0.036P] where P = (F_o² + 2F_c²)/3
3341 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₀H₁₇NO	γ = 71.385 (3)°
M_r = 167.25	V = 499.43 (4) Å³
Triclinic, P1	Z = 2
a = 7.5670 (3) Å	Mo Kα radiation
b = 7.7208 (3) Å	µ = 0.07 mm⁻¹
c = 9.3072 (4) Å	T = 296 K
α = 81.212 (3)°	0.09 × 0.06 × 0.05 mm
β = 76.590 (3)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3341 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2134 reflections with I > 2σ(I)
T_min = 0.994, T_max = 0.997	R_int = 0.022
13971 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.24 e Å⁻³
3341 reflections	Δρ_min = −0.14 e Å⁻³
118 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.60371 (16)	−0.14350 (15)	0.37650 (16)	0.0794 (5)
N1	0.67895 (14)	0.00174 (14)	0.37695 (13)	0.0552 (4)
C1	0.94463 (15)	0.11492 (15)	0.25083 (13)	0.0425 (3)
C2	1.12581 (16)	0.05523 (17)	0.17581 (14)	0.0492 (3)
C3	1.26022 (18)	0.1703 (2)	0.1444 (2)	0.0680 (5)
C4	1.1923 (2)	0.3358 (2)	0.2335 (2)	0.0772 (6)
C5	0.9848 (2)	0.42925 (19)	0.2342 (2)	0.0656 (5)
C6	0.85762 (15)	0.30698 (15)	0.30624 (14)	0.0458 (3)
C7	0.83019 (17)	−0.01188 (16)	0.27932 (16)	0.0505 (4)
C8	1.2169 (2)	−0.1322 (2)	0.11773 (18)	0.0689 (5)
C9	0.8338 (2)	0.2967 (2)	0.47500 (17)	0.0641 (5)
C10	0.66297 (19)	0.40088 (18)	0.26268 (19)	0.0627 (5)
H1	0.509 (3)	−0.126 (3)	0.450 (3)	0.107 (7)*
H3A	1.27880	0.21180	0.03980	0.0820*
H3B	1.38250	0.09430	0.16530	0.0820*
H4A	1.21150	0.29760	0.33440	0.0930*
H4B	1.26500	0.42070	0.19030	0.0930*
H5A	0.96760	0.46760	0.13290	0.0790*
H5B	0.94450	0.53850	0.28720	0.0790*
H7	0.866 (2)	−0.116 (2)	0.2260 (19)	0.074 (5)*
H8A	1.29070	−0.21220	0.18590	0.1030*
H8B	1.29810	−0.12140	0.02290	0.1030*
H8C	1.11960	−0.18180	0.10750	0.1030*
H9A	0.75450	0.22010	0.52080	0.0960*
H9B	0.77580	0.41760	0.50780	0.0960*
H9C	0.95610	0.24580	0.50220	0.0960*
H10A	0.57850	0.32850	0.30550	0.0940*
H10B	0.67810	0.41230	0.15670	0.0940*
H10C	0.61080	0.52050	0.29870	0.0940*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0698 (7)	0.0627 (6)	0.1080 (10)	−0.0392 (5)	0.0201 (6)	−0.0293 (6)
N1	0.0466 (5)	0.0490 (5)	0.0702 (8)	−0.0218 (4)	0.0031 (5)	−0.0113 (5)
C1	0.0377 (5)	0.0448 (5)	0.0424 (6)	−0.0118 (4)	−0.0047 (4)	−0.0018 (4)
C2	0.0404 (5)	0.0555 (6)	0.0453 (7)	−0.0109 (5)	−0.0021 (5)	−0.0023 (5)
C3	0.0404 (6)	0.0793 (9)	0.0796 (11)	−0.0225 (6)	0.0014 (6)	−0.0022 (8)
C4	0.0539 (8)	0.0782 (10)	0.1078 (14)	−0.0362 (7)	−0.0069 (8)	−0.0105 (9)
C5	0.0586 (8)	0.0526 (7)	0.0853 (11)	−0.0243 (6)	−0.0051 (7)	−0.0019 (7)
C6	0.0399 (5)	0.0433 (5)	0.0530 (7)	−0.0131 (4)	−0.0055 (5)	−0.0046 (5)
C7	0.0459 (6)	0.0439 (6)	0.0588 (8)	−0.0136 (4)	0.0000 (5)	−0.0105 (5)
C8	0.0548 (7)	0.0692 (9)	0.0673 (10)	−0.0053 (6)	0.0068 (7)	−0.0172 (7)
C9	0.0694 (8)	0.0688 (8)	0.0574 (8)	−0.0237 (7)	−0.0063 (7)	−0.0171 (7)
C10	0.0491 (7)	0.0496 (7)	0.0859 (11)	−0.0041 (5)	−0.0184 (7)	−0.0100 (6)

Geometric parameters (Å, º) top

O1—N1	1.4113 (16)	C4—H4A	0.9700
O1—H1	0.86 (3)	C4—H4B	0.9700
N1—C7	1.2714 (18)	C5—H5A	0.9700
C1—C6	1.5334 (16)	C5—H5B	0.9700
C1—C7	1.4608 (18)	C7—H7	0.942 (15)
C1—C2	1.3530 (18)	C8—H8A	0.9600
C2—C8	1.5136 (19)	C8—H8B	0.9600
C2—C3	1.506 (2)	C8—H8C	0.9600
C3—C4	1.514 (2)	C9—H9A	0.9600
C4—C5	1.503 (2)	C9—H9B	0.9600
C5—C6	1.534 (2)	C9—H9C	0.9600
C6—C9	1.532 (2)	C10—H10A	0.9600
C6—C10	1.538 (2)	C10—H10B	0.9600
C3—H3A	0.9700	C10—H10C	0.9600
C3—H3B	0.9700

N1—O1—H1	103.3 (15)	H4A—C4—H4B	108.00
O1—N1—C7	111.09 (11)	C4—C5—H5A	109.00
C2—C1—C6	122.81 (11)	C4—C5—H5B	109.00
C6—C1—C7	119.71 (10)	C6—C5—H5A	109.00
C2—C1—C7	117.48 (11)	C6—C5—H5B	109.00
C1—C2—C8	124.63 (12)	H5A—C5—H5B	108.00
C3—C2—C8	112.81 (12)	N1—C7—H7	113.3 (10)
C1—C2—C3	122.55 (12)	C1—C7—H7	121.4 (10)
C2—C3—C4	113.94 (13)	C2—C8—H8A	109.00
C3—C4—C5	109.66 (13)	C2—C8—H8B	109.00
C4—C5—C6	113.33 (12)	C2—C8—H8C	109.00
C1—C6—C9	110.71 (10)	H8A—C8—H8B	109.00
C1—C6—C10	110.80 (10)	H8A—C8—H8C	109.00
C5—C6—C9	109.05 (12)	H8B—C8—H8C	109.00
C5—C6—C10	106.66 (11)	C6—C9—H9A	109.00
C9—C6—C10	109.18 (11)	C6—C9—H9B	109.00
C1—C6—C5	110.33 (10)	C6—C9—H9C	109.00
N1—C7—C1	125.29 (12)	H9A—C9—H9B	109.00
C2—C3—H3A	109.00	H9A—C9—H9C	109.00
C2—C3—H3B	109.00	H9B—C9—H9C	110.00
C4—C3—H3A	109.00	C6—C10—H10A	109.00
C4—C3—H3B	109.00	C6—C10—H10B	109.00
H3A—C3—H3B	108.00	C6—C10—H10C	109.00
C3—C4—H4A	110.00	H10A—C10—H10B	110.00
C3—C4—H4B	110.00	H10A—C10—H10C	109.00
C5—C4—H4A	110.00	H10B—C10—H10C	109.00
C5—C4—H4B	110.00

O1—N1—C7—C1	−179.61 (12)	C7—C1—C6—C10	−49.10 (16)
C6—C1—C2—C3	2.0 (2)	C2—C1—C7—N1	161.31 (13)
C6—C1—C2—C8	−179.34 (12)	C6—C1—C7—N1	−18.5 (2)
C7—C1—C2—C3	−177.72 (13)	C1—C2—C3—C4	13.8 (2)
C7—C1—C2—C8	0.89 (19)	C8—C2—C3—C4	−165.00 (13)
C2—C1—C6—C5	13.24 (17)	C2—C3—C4—C5	−44.02 (19)
C2—C1—C6—C9	−107.58 (14)	C3—C4—C5—C6	61.57 (18)
C2—C1—C6—C10	131.13 (13)	C4—C5—C6—C1	−45.18 (17)
C7—C1—C6—C5	−167.00 (12)	C4—C5—C6—C9	76.62 (16)
C7—C1—C6—C9	72.19 (15)	C4—C5—C6—C10	−165.59 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.86 (3)	2.02 (3)	2.8346 (18)	158 (2)
C9—H9A···N1	0.96	2.57	3.1979 (19)	123
C10—H10A···N1	0.96	2.43	3.0762 (17)	125

Symmetry code: (i) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₇NO
M_r	167.25
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.5670 (3), 7.7208 (3), 9.3072 (4)
α, β, γ (°)	81.212 (3), 76.590 (3), 71.385 (3)
V (Å³)	499.43 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.09 × 0.06 × 0.05

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.994, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	13971, 3341, 2134
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.766

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.191, 1.06
No. of reflections	3341
No. of parameters	118
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.14

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱ	0.86 (3)	2.02 (3)	2.8346 (18)	158 (2)
C9—H9A···N1	0.96	2.57	3.1979 (19)	123
C10—H10A···N1	0.96	2.43	3.0762 (17)	125

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

PTM and SJJ thank the DST India (FIST programme) for the use of the diffractometer at the School of Chemistry, Bharathidasan University, Tiruchirappalli, Tamilnadu, India.

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