Acta Cryst. (2011). E67, o2732 [ doi:10.1107/S1600536811037895 ]
In the crystal of the title compound C10H17NO, synthesized by the reaction of ![[beta]](/logos/entities/beta_rmgif.gif)
-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-HN interactions. The cyclohexene ring has the typical half-chair conformation.
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.
The H atoms attached to C7 and O1 were located from a difference Fourier map and were refined freely. The remaining H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with Uiso(H) set at 1.2Ueq(C) except for the methyl hydrogen atoms which were refined with Uiso(H) set at 1.5Ueq(C).
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).
![[Figure 1]](./zs2144fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids drawn at the 50% probability level. |
![[Figure 2]](./zs2144fig2thm.gif)
| Fig. 2. The centrosymmetric R22(6) hydrogen-bonded dimer units, with hydrogen bonds shown as dashed lines. For symmetry code (i), see Table 1. |
| C10H17NO | Z = 2 |
| Mr = 167.25 | F(000) = 184 |
| Triclinic, P1 | Dx = 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 |
| Bruker SMART APEXII CCD area-detector diffractometer | 3341 independent reflections |
| Radiation source: fine-focus sealed tube | 2134 reflections with I > 2σ(I) |
| graphite | Rint = 0.022 |
| φ and ω scans | θmax = 33.0°, θmin = 2.3° |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −11→11 |
| Tmin = 0.994, Tmax = 0.997 | k = −11→11 |
| 13971 measured reflections | l = −12→13 |
| 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(Fo2) + (0.0999P)2 + 0.036P] where P = (Fo2 + 2Fc2)/3 |
| 3341 reflections | (Δ/σ)max < 0.001 |
| 118 parameters | Δρmax = 0.24 e Å−3 |
| 0 restraints | Δρmin = −0.14 e Å−3 |
| C10H17NO | γ = 71.385 (3)° |
| Mr = 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)° |
| Bruker SMART APEXII CCD area-detector diffractometer | 3341 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2008) | 2134 reflections with I > 2σ(I) |
| Tmin = 0.994, Tmax = 0.997 | Rint = 0.022 |
| 13971 measured reflections | θmax = 33.0° |
| R[F2 > 2σ(F2)] = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.191 | Δρmax = 0.24 e Å−3 |
| S = 1.06 | Δρmin = −0.14 e Å−3 |
| 3341 reflections | Absolute structure: ? |
| 118 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| 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* |
| 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) |
| 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) |
| 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 codes: (i) −x+1, −y, −z+1. |
| 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 codes: (i) −x+1, −y, −z+1. |
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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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···Noxime hydrogen-bonding interactions.