Crystal structures of two (±)-exo-N-isobornyl­acetamides

Stepanovs, D.; Posevins, D.; Turks, M.

doi:10.1107/S2056989015015984

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ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages 1117-1120

doi:10.1107/S2056989015015984

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Crystal structures of two (±)-exo-N-isobornylacetamides

Dmitrijs Stepanovs,^a,^b ^* Daniels Posevins ^b and Maris Turks ^b ^*

^aLatvian Institute of Organic Synthesis, Aizkraukles 21, Riga, LV-1006, Latvia, and ^bInstitute of Technology of Organic Chemistry, Faculty of Materials Science and Applied Chemistry, Riga Technical University, P. Valdena 3/7, Riga, LV-1048, Latvia
^*Correspondence e-mail: d_stepanovs@osi.lv, maris_turks@ktf.rtu.lv

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 12 August 2015; accepted 26 August 2015; online 12 September 2015)

The title compounds consist of a bornane skeleton with attached acetamide, C₁₂H₂₁NO (±)-(1) {systematic name: (±)-N-[(1RS,2RS,4RS)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl]acetamide}, and chloroacetamide, C₁₂H₂₀ClNO (±)-(2) {systematic name: (±)-2-chloro-N-[(1RS,2RS,4RS)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl]acetamide}, functionalities to the 2-exo-position. The crystal structure of the first monoclinic polymorph of (±)-(1) has been reported previously [Ung et al. (2014 ). Monatsh. Chem. 145, 983–992]. Compound (±)-(1) crystallizes in the space group P2₁/n with two independent molecules in the asymmetric unit, in contrast to the above-mentioned polymorph which crystallized in the space group C2/c with one molecule in the asymmetric unit. In the title compounds, the bicyclic bornane moieties have normal geometries. In the crystals of both compounds, molecules are linked by N—H⋯O hydrogen bonds, reinforced by C—H⋯O contacts, forming trans-amide chains propagating along the a-axis direction. In the case of compound (±)-(1), neighbouring chains are linked by further C—H⋯O contacts, forming double-chain ribbons along [100].

Keywords: crystal structure; Ritter reaction; (±)-exo-N-isobornylacetamides; polymorph; hydrogen bonding.

CCDC references: 1420761; 1420760

1. Chemical context

Isobornylamine-derived amides have recently been described as useful antimycobacterial agents (Stavrakov et al., 2014a ,b ). Promising biological activity profiles have been also discovered for other bornane derivatives such as 2-arylbornanes (Duclos et al., 2008 ), camphor oximes (Schenone et al., 2000 ), bornyl (3,4,5-trihydroxy)-cinnamate (Steinbrecher et al., 2008 ) and others. There is no doubt that isobornylamine derivatives are chemically related to terpenoids camphor (Seebaluck et al., 2015 ) and borneol (Horváthová et al., 2012 ), which are well known for their biological activities. On the other hand, compounds containing the bornane skeleton are frequently used as chiral building blocks for various ligands, catalysts and chiral auxiliaries (Chelucci, 2006 ; Langlois & Kouklovsky, 2009 ; Ramón & Yus, 2007 ). In light of the aforementioned facts, there is a vast interest in developing new synthetic protocols for the synthesis of compounds of this class and in their structural studies. We have recently reported an application of the Ritter reaction (Jiang et al., 2014 ) in the synthesis of amide-derivatized heterocycles (Turks et al., 2012 ). Hence, we identified the possibility to obtain isobornylamine derived amides (±)-(1) and (±)-(2) from borneol in the direct Ritter reaction. When the optically active (−)-borneol was submitted to standard Ritter reaction conditions, the expected compounds were isolated in acceptable yields albeit in the racemic form. A similar type of racemization due to a 6,2-hydride shift was described in the Ritter reaction of (−)-bornyl acetate (Hanzawa et al., 2012 .). Previously, compounds (±)-(1) and (±)-(2) have been obtained as side products in a cationic rearrangement of (−)-β-pinene in the presence of the corresponding nitriles (Ung et al., 2014).

2. Structural commentary

The title compounds consist of a 1,7,7-trimethylbicyclo[2.2.1]heptane (bornane or camphane) skeleton with attached acetamide [(±)-(1)] and chloroacetamide [(±)-(2)] functionalities in the 2-exo-position. The asymmetric unit of compound (±)-(1) (Fig. 1) contains two independent molecules having coincident geometry (r.m.s. deviation 0.057 Å). Compound (±)-(2) (Fig. 2) contains one molecule in the asymmetric unit. The bond lengths and angles in both compounds are close to those observed for the first monoclinic polymorph of compound (±)-(1) (Ung et al., 2014).

Figure 1
The molecular structure of the two independent molecules of compound (±)-(1), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
The molecular structure of compound (±)-(2), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystals of both compounds, molecules are linked by N—H⋯O hydrogen bonds, reinforced by C—H⋯O contacts, forming trans-amide chains propagating along the a axis direction (Figs. 3 and 4 and Tables 1 and 2). In the case of compound (±)-(1), neighbouring chains are linked by further C—H⋯O contacts, forming ribbons along [100]; see Fig. 3 and Table 1.

Table 1
Hydrogen-bond geometry (Å, °) for (±)-(1)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1Aⁱ	0.85 (2)	2.06 (2)	2.900 (2)	170 (2)
N1A—H1AN⋯O1ⁱⁱ	0.87 (2)	2.03 (2)	2.886 (2)	172 (2)
C8A—H8A1⋯O1ⁱⁱ	0.98	2.57	3.524 (3)	165
C12—H12C⋯O1ⁱⁱ	0.98	2.52	3.468 (3)	164
Symmetry codes: (i) -x+1, -y, -z; (ii) -x, -y, -z.

Table 2
Hydrogen-bond geometry (Å, °) for (±)-(2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.79 (3)	2.21 (3)	2.983 (2)	168 (2)
C12—H12A⋯O1ⁱ	0.97	2.36	3.238 (3)	151
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

Figure 3
The crystal packing of compound (±)-(1), viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1

for details). For clarity, only H atoms involved in these interactions have been included.

Figure 4
The crystal packing of compound (±)-(2), viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 2

for details). For clarity, only H atoms involved in these interactions have been included.

4. Database survey

A search of the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014 ) for substituted bornanes gave 1517 hits (excluding organometallics). 119 structures are substituted at the 2-position. Only two of these are amides, viz. the previously reported polymorph of (±)-(1) (LOPQEO: Ung et al., 2014) and 2,2,2-triphenyl-N-(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)acetamide (TOQWED: Prusinowska et al., 2015 ).

5. Synthesis and crystallization

Compound (±)-(1): (−)-Borneol (463 mg, 3 mmol, 1 equiv.) was added to a stirred solution of acetonitrile (790 µL, 15 mmol, 5.0 equiv.) in glacial acetic acid (7.0 ml) and conc. H₂SO₄ (3.07 g, 30 mmol, 10.0 equiv.). The resulting reaction mixture was stirred at 343 K for 16 h (TLC control). The reaction mixture was cooled to 273 K and poured into a vigorously stirred 10% aqueous solution of NaOH (30–40 mL) at 273 K. Ethyl acetate (30 mL) was added and the phases were separated. The aqueous phase was extracted with ethyl acetate (3 × 20 mL). The combined organic phase was washed with brine, dried over anhydrous Na₂SO₄, filtered and evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography to provide (±)-(1) (yield: 319 mg, 55%). The NMR data of (±)-(1) correspond fully to those reported earlier (Ung et al., 2014): ¹H NMR (300 MHz, CDCl₃) δ (p.p.m.): 5.44 (br s, 1H), 3.87 (td, J = 9.0, 5.2 Hz, 1H), 1.97–1.77 (m, 4H), 1.73–1.61 (m, 2H), 1.60–1.46 (m, 2H), 1.32–1.20 (m, 1H), 1.18–1.07 (m, 1H), 0.88 (s, 3H), 0.81 (s, 3H), 0.80 (s, 3H); ¹³C NMR (75.5 MHz, CDCl₃) δ (p.p.m.): 169.35, 56.81, 48.87, 47.14, 44.92, 39.15, 36.02, 27.06, 23.69, 20.38, 20.35, 11.77. GC–MS (C₁₂H₂₁NO): t_R = 5.92 min; m/z: calculated 195.2; found 195.1. (GC–MS method: column: HP5 (5% phenyl methyl siloxane), 30 m × 0.25 mm ID, 0.25 µm; column temp.: 323 K (hold for 2 min) to 583 K at 323 K min⁻¹ (hold at 583 K for 3 min); injector/detector: 523 K/503 K; carrier gas: helium at 1.0 mL min⁻¹, linear velocity; injection mode: splitless (solvent delay: 3 min); injection volume: 1 µL). X-ray quality single crystals were obtained by slow evaporation of a solution of (±)-(1) in hexanes/ethyl acetate (2:1).

Compound (±)-(2): (−)-Borneol (463 mg, 3 mmol, 1 equiv.) was added to a stirred solution of chloroacetonitrile (950 µL, 15 mmol, 5.0 equiv.) in glacial acetic acid (7.0 ml) and conc. H₂SO₄ (3.07 g, 30 mmol, 10.0 equiv.). The resulting reaction mixture was stirred at 343 K for 16 h (TLC control). The reaction mixture was cooled to 273 K and poured into a vigorously stirred 10% aqueous solution of NaOH (30-40 mL) at 273 K. Ethyl acetate (30 mL) was added and the phases were separated. The aqueous phase was extracted with ethyl acetate (3 × 20 mL). The combined organic phase was washed with brine, dried over anhydrous Na₂SO₄, filtered and evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography to provide (±)-(2) (yield: 318 mg, 46%). The NMR data of (±)-(2) fully correspond to those reported earlier (Ung et al., 2014): ¹H NMR (300 MHz, CDCl₃) δ (p.p.m.): 6.63 (br s, 1H), 4.03 (d, J = 1.5 Hz, 2H), 3.88 (td, J = 9.1, 4.9 Hz, 1H), 1.87 (dd, J = 13.3, 9.1 Hz, 1H), 1.80–1.52 (m, 4H), 1.35–1.23 (m, 1H), 1.22–1.10 (m, 1H), 0.94 (s, 3H), 0.86–0.83 (m, 6H); ¹³C NMR (75.5 MHz, CDCl₃) δ (p.p.m.): 164.97, 57.12, 48.69, 47.21, 45.01, 43.00, 39.01, 35.95, 27.10, 20.33, 20.19, 11.82. GC–MS (C₁₂H₂₀³⁵ClNO): t_R = 6.21 min; m/z: calculated 229.1; found 229.1. (GC–MS method: vide supra). X-ray quality single crystals were obtained by slow evaporation of a solution of (±)-(2) in hexanes/ethyl acetate (2:1).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. For both compounds, the H atom on the amino group were located in difference Fourier maps and freely refined, and the C-bound H atoms were positioned geometrically and refined as riding on their parent atoms: C—H = 0.93–0.97 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms. Reflection (0,1,1) whose intensity was affected by the beam-stop was removed from the final refinement of compound (±)-(1).

Table 3
Experimental details

	(±)-(1)	(±)-(2)
Crystal data
Chemical formula	C₁₂H₂₁NO	C₁₂H₂₀ClNO
M_r	195.30	229.74
Crystal system, space group	Monoclinic, P2₁/n	Orthorhombic, Pcab
Temperature (K)	173	173
a, b, c (Å)	9.6820 (6), 10.6540 (3), 23.3676 (7)	9.6852 (2), 10.7589 (3), 23.7261 (8)
α, β, γ (°)	90, 97.184 (10), 90	90, 90, 90
V (Å³)	2391.49 (19)	2472.31 (12)
Z	8	8
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.07	0.29
Crystal size (mm)	0.18 × 0.12 × 0.09	0.35 × 0.10 × 0.09

Data collection
Diffractometer	Nonius KappaCCD	Nonius KappaCCD
No. of measured, independent and observed [I > 2σ(I)] reflections	7908, 4320, 2637	6757, 3611, 1854
R_int	0.056	0.097
(sin θ/λ)_max (Å⁻¹)	0.600	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.159, 1.05	0.073, 0.160, 1.02
No. of reflections	4320	3611
No. of parameters	269	143
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.20	0.51, −0.38
Computer programs: KappaCCD Server Software (Nonius, 1997 ), DENZO and SCALEPACK (Otwinowski & Minor, 1997 ), SIR2011 (Burla et al., 2012 ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ), SHELXL97 (Sheldrick, 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1420761; 1420760

Crystal structure: contains datablocks 1, 2, Global. DOI: 10.1107/S2056989015015984/su5191sup1.cif

Structure factors: contains datablock 1. DOI: 10.1107/S2056989015015984/su51911sup2.hkl

Structure factors: contains datablock 2. DOI: 10.1107/S2056989015015984/su51912sup3.hkl

Supporting information file. DOI: 10.1107/S2056989015015984/su51911sup4.cml

Supporting information file. DOI: 10.1107/S2056989015015984/su51912sup5.cml

checkCIF report

Chemical context top

Isobornylamine-derived amides have recently been described as useful antimycobacterial agents (Stavrakov et al., 2014a,b). Promising biological activity profiles have been also discovered for other bornane derivatives such as 2-arylbornanes (Duclos et al., 2008), camphor oximes (Schenone et al., 2000), bornyl (3,4,5-trihydroxy)-cinnamate (Steinbrecher et al., 2008) and others. There is no doubt that isobornylamine derivatives are chemically related to terpenoids camphor (Seebaluck et al., 2015) and borneol (Horváthová et al., 2012), which are well known for their biological activities. On the other hand, compounds containing the bornane skeleton are frequently used as chiral building blocks for various ligands, catalysts and chiral auxiliaries (Chelucci, 2006; Langlois & Kouklovsky, 2009; Ramón & Yus, 2007). In light of the aforementioned facts, there is a vast interest in novel synthetic protocols for the synthesis of compounds of this class and in their structural studies. We have recently reported an application of the Ritter reaction (Jiang et al., 2014) in the synthesis of amide-derivatized heterocycles (Turks et al., 2012). Hence, we identified the possibility to obtain isobornylamine derived amides (±)-(1) and (±)-(2) from borneol in the direct Ritter reaction. When the optically active (-)-borneol was submitted to standard Ritter reaction conditions, the expected compounds were isolated in acceptable yields albeit in the racemic form. A similar type of racemization due to a 6,2-hydride shift was described in the Ritter reaction of (-)-bornyl acetate (Hanzawa et al., 2012.). Previously, compounds (±)-(1) and (±)-(2) have been obtained as side products in a cationic rearrangement of (-)-β-pinene in the presence of the corresponding nitriles (Ung et al., 2014).

Structural commentary top

The title compounds consist of a 1,7,7-trimethylbicyclo[2.2.1]heptane (bornane or camphane) skeleton with attached acetamide [(±)-(1)] and chloroacetamide [(±)-(2)] functionalities in the 2-exo-position.The asymmetric unit of compound (±)-(1) (Fig. 1) contains two independent molecules having coincident geometry. Compound (±)-(2) (Fig. 2) contains one molecule in the asymmetric unit. The bond lengths and angles in both compounds are close to those observed for the first monoclinic polymorph of compound (±)-(1) (Ung et al., 2014).

Supramolecular features top

In the crystals of both compounds, molecules are linked by N—H···O hydrogen bonds, reinforced by C—H···O contacts, forming trans-amide chains propagating along the a axis direction (Figs. 3 and 4 and Tables 1 and 2). In the case of compound (±)-(1), neighbouring chains are linked by further C—H···O contacts, forming ribbons along [100]; see Fig. 3 and Table 1.

Database survey top

A search of the Cambridge Structural Database (Version 5.36; Groom & Allen, 2014) for substituted bornanes gave 1517 hits (excluding organometallics). 119 structures are substituted at the 2-position. Only two of these are amides, viz. the previously reported polymorph of (±)-(1) (LOPQEO: Ung et al., 2014) and 2,2,2-triphenyl-N-(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)acetamide (TOQWED: Prusinowska et al., 2015).

Synthesis and crystallization top

Compound (±)-(1): (-)-Borneol (463 mg, 3 mmol, 1 equiv.) was added to a stirred solution of acetonitrile (790 µL, 15 mmol, 5.0 equiv.) in glacial acetic acid (7.0 ml) and conc. H₂SO₄ (3.07 g, 30 mmol, 10.0 equiv.). The resulting reaction mixture was stirred at 343 K for 16 h (TLC control). The reaction mixture was cooled to 273 K and poured into a vigorously stirred ~10% aqueous solution of NaOH (30–40 mL) at 273 K. Ethyl acetate (30 mL) was added and the phases were separated. The aqueous phase was extracted with ethyl acetate (3 × 20 mL). The combined organic phase was washed with brine, dried over anhydrous Na₂SO₄, filtered and evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography to provide (±)-(1) (yield: 319 mg, 55%). The NMR data of (±)-(1) correspond fully to those reported earlier (Ung et al., 2014): ¹H NMR (300 MHz, CDCl₃) δ (p.p.m.): 5.44 (br s, 1H), 3.87 (td, J = 9.0, 5.2 Hz, 1H), 1.97–1.77 (m, 4H), 1.73–1.61 (m, 2H), 1.60–1.46 (m, 2H), 1.32–1.20 (m, 1H), 1.18–1.07 (m, 1H), 0.88 (s, 3H), 0.81 (s, 3H), 0.80 (s, 3H); ¹³C NMR (75.5 MHz, CDCl₃) δ (p.p.m.): 169.35, 56.81, 48.87, 47.14, 44.92, 39.15, 36.02, 27.06, 23.69, 20.38, 20.35, 11.77. GC–MS (C₁₂H₂₁NO): t_R = 5.92 min; m/z: calculated 195.2; found 195.1. (GC–MS Method: Column: HP5 (5% phenyl methyl siloxane), 30 m × 0.25 mm ID, 0.25 µm; Column temp.: 323 K (hold for 2 min) to 583 K at 323 K min^-1 (hold at 583 K for 3 min); injector/detector: 523 K/503 K; Carrier gas: helium at 1.0 mL min^-1, linear velocity; injection mode: splitless (solvent delay: 3 min); Injection volume: 1 µL). X-ray quality single crystals were obtained by slow evaporation of a solution of (±)-(1) in hexanes/ethyl acetate (2:1).

Compound (±)-(2): (-)-Borneol (463 mg, 3 mmol, 1 equiv.) was added to a stirred solution of chloroacetonitrile (950 µL, 15 mmol, 5.0 equiv.) in glacial acetic acid (7.0 ml) and conc. H₂SO₄ (3.07 g, 30 mmol, 10.0 equiv.). The resulting reaction mixture was stirred at 343 K for 16 h (TLC control). The reaction mixture was cooled to 273 K and poured into a vigorously stirred ~10% aqueous solution of NaOH (30-40 mL) at 273 K. Ethyl acetate (30 mL) was added and the phases were separated. The aqueous phase was extracted with ethyl acetate (3 × 20 mL). The combined organic phase was washed with brine, dried over anhydrous Na₂SO₄, filtered and evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography to provide (±)-(2) (yield: 318 mg, 46%). The NMR data of (±)-(2) fully correspond to those reported earlier (Ung et al., 2014): ¹H NMR (300 MHz, CDCl₃) δ (p.p.m.): 6.63 (br s, 1H), 4.03 (d, J = 1.5 Hz, 2H), 3.88 (td, J = 9.1, 4.9 Hz, 1H), 1.87 (dd, J = 13.3, 9.1 Hz, 1H), 1.80–1.52 (m, 4H), 1.35–1.23 (m, 1H), 1.22–1.10 (m, 1H), 0.94 (s, 3H), 0.86–0.83 (m, 6H); ¹³C NMR (75.5 MHz, CDCl₃) δ (p.p.m.): 164.97, 57.12, 48.69, 47.21, 45.01, 43.00, 39.01, 35.95, 27.10, 20.33, 20.19, 11.82. GC—MS (C₁₂H₂₀³⁵ClNO): t_R = 6.21 min; m/z: calculated 229.1; found 229.1. (GC–MS method: vide supra). X-ray quality single crystals were obtained by slow evaporation of a solution of (±)-(2) in hexanes/ethyl acetate (2:1).

Refinement top

Computing details top

For both compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the two independent molecules of compound (±)-(1), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of compound (±)-(2), showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The crystal packing of compound (±)-(1), viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details). For clarity, only H atoms involved in these interactions have been included.
	Fig. 4. The crystal packing of compound (±)-(2), viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 2 for details). For clarity, only H atoms involved in these interactions have been included.

(1) (±)-N-[(1RS,2RS,4RS)-1,7,7-Trimethylbicyclo[2.2.1]heptan-2-yl]acetamide top

Crystal data top

C₁₂H₂₁NO	F(000) = 864
M_r = 195.30	D_x = 1.085 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 23028 reflections
a = 9.6820 (6) Å	θ = 1.0–30.0°
b = 10.6540 (3) Å	µ = 0.07 mm⁻¹
c = 23.3676 (7) Å	T = 173 K
β = 97.184 (10)°	Plate, colourless
V = 2391.49 (19) Å³	0.18 × 0.12 × 0.09 mm
Z = 8

Data collection top

Nonius KappaCCD diffractometer	2637 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.056
Graphite monochromator	θ_max = 25.3°, θ_min = 2.2°
φ and ω scan	h = −11→11
7908 measured reflections	k = −12→11
4320 independent reflections	l = −28→27

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0684P)² + 0.5097P] where P = (F_o² + 2F_c²)/3
4320 reflections	(Δ/σ)_max < 0.001
269 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₂H₂₁NO	V = 2391.49 (19) Å³
M_r = 195.30	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6820 (6) Å	µ = 0.07 mm⁻¹
b = 10.6540 (3) Å	T = 173 K
c = 23.3676 (7) Å	0.18 × 0.12 × 0.09 mm
β = 97.184 (10)°

Data collection top

Nonius KappaCCD diffractometer	2637 reflections with I > 2σ(I)
7908 measured reflections	R_int = 0.056
4320 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.159	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.37 e Å⁻³
4320 reflections	Δρ_min = −0.20 e Å⁻³
269 parameters

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) 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	−0.02258 (14)	0.12729 (16)	0.06523 (7)	0.0422 (5)
N1	0.18985 (18)	0.21667 (19)	0.07437 (8)	0.0296 (5)
H1N	0.276 (2)	0.204 (2)	0.0728 (9)	0.036 (7)*
C1	0.1084 (3)	0.6083 (3)	0.09760 (13)	0.0543 (8)
H1A	0.0660	0.6280	0.0579	0.065*
H1B	0.1171	0.6865	0.1206	0.065*
C2	0.0227 (2)	0.5082 (2)	0.12569 (12)	0.0474 (7)
H2A	−0.0068	0.5399	0.1621	0.057*
H2B	−0.0610	0.4837	0.0993	0.057*
C3	0.1236 (2)	0.3969 (2)	0.13719 (10)	0.0346 (6)
C4	0.1376 (2)	0.3440 (2)	0.07640 (10)	0.0311 (6)
H4	0.0440	0.3475	0.0529	0.037*
C5	0.2338 (2)	0.4415 (2)	0.05134 (11)	0.0402 (6)
H5A	0.3248	0.4039	0.0460	0.048*
H5B	0.1898	0.4752	0.0140	0.048*
C6	0.2501 (2)	0.5434 (2)	0.09772 (11)	0.0436 (7)
H6	0.3292	0.6024	0.0947	0.052*
C7	0.2638 (2)	0.4669 (2)	0.15414 (10)	0.0385 (6)
C8	0.3926 (2)	0.3821 (3)	0.16342 (12)	0.0478 (7)
H8A	0.3995	0.3333	0.1283	0.072*
H8B	0.3844	0.3248	0.1956	0.072*
H8C	0.4762	0.4339	0.1722	0.072*
C9	0.2675 (3)	0.5485 (3)	0.20856 (12)	0.0583 (8)
H9A	0.3534	0.5981	0.2135	0.087*
H9B	0.2645	0.4945	0.2423	0.087*
H9C	0.1870	0.6050	0.2046	0.087*
C10	0.0805 (3)	0.3019 (3)	0.17942 (12)	0.0481 (7)
H10D	0.0789	0.3419	0.2171	0.072*
H10E	0.1471	0.2323	0.1831	0.072*
H10F	−0.0126	0.2700	0.1654	0.072*
C11	0.1054 (2)	0.1169 (2)	0.06847 (9)	0.0318 (6)
C12	0.1737 (2)	−0.0091 (2)	0.06613 (12)	0.0422 (7)
H12A	0.1673	−0.0544	0.1022	0.063*
H12B	0.2719	0.0022	0.0610	0.063*
H12C	0.1267	−0.0574	0.0337	0.063*
O1A	0.52606 (14)	−0.16700 (16)	−0.05366 (7)	0.0413 (5)
N1A	0.31245 (18)	−0.08247 (18)	−0.07554 (8)	0.0297 (5)
H1AN	0.223 (2)	−0.092 (2)	−0.0758 (9)	0.035 (6)*
C1A	0.3751 (3)	0.2963 (3)	−0.12778 (15)	0.0615 (8)
H1A1	0.4035	0.3332	−0.0892	0.074*
H1A2	0.3675	0.3640	−0.1570	0.074*
C2A	0.4775 (2)	0.1949 (2)	−0.14177 (13)	0.0523 (8)
H2A1	0.5552	0.1864	−0.1102	0.063*
H2A2	0.5161	0.2145	−0.1780	0.063*
C3A	0.3881 (2)	0.0737 (2)	−0.14821 (11)	0.0396 (6)
C4A	0.3603 (2)	0.0434 (2)	−0.08641 (10)	0.0343 (6)
H4A	0.4474	0.0600	−0.0597	0.041*
C5A	0.2472 (3)	0.1450 (3)	−0.07462 (12)	0.0463 (7)
H5A1	0.1567	0.1053	−0.0702	0.056*
H5A2	0.2786	0.1956	−0.0399	0.056*
C6A	0.2383 (3)	0.2240 (3)	−0.12928 (14)	0.0568 (8)
H6A	0.1537	0.2786	−0.1354	0.068*
C7A	0.2459 (2)	0.1260 (3)	−0.17734 (11)	0.0418 (7)
C8A	0.1271 (2)	0.0305 (3)	−0.18521 (12)	0.0530 (8)
H8A1	0.1113	−0.0029	−0.1475	0.079*
H8A2	0.1518	−0.0383	−0.2098	0.079*
H8A3	0.0421	0.0715	−0.2033	0.079*
C9A	0.2545 (3)	0.1849 (4)	−0.23710 (14)	0.0819 (11)
H9A1	0.1685	0.2313	−0.2495	0.123*
H9A2	0.2664	0.1184	−0.2650	0.123*
H9A3	0.3340	0.2424	−0.2347	0.123*
C10A	0.4535 (3)	−0.0307 (3)	−0.17793 (12)	0.0485 (7)
H10A	0.3955	−0.1061	−0.1779	0.073*
H10B	0.5462	−0.0483	−0.1576	0.073*
H10C	0.4618	−0.0063	−0.2178	0.073*
C11A	0.3980 (2)	−0.1770 (2)	−0.05835 (9)	0.0326 (6)
C12A	0.3303 (2)	−0.2983 (3)	−0.04552 (14)	0.0577 (8)
H12D	0.3754	−0.3321	−0.0089	0.087*
H12E	0.3397	−0.3585	−0.0765	0.087*
H12F	0.2314	−0.2838	−0.0428	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0203 (8)	0.0470 (12)	0.0600 (12)	−0.0052 (7)	0.0079 (7)	−0.0016 (9)
N1	0.0170 (9)	0.0367 (13)	0.0359 (12)	−0.0036 (9)	0.0059 (7)	−0.0039 (10)
C1	0.0598 (17)	0.0345 (17)	0.067 (2)	0.0022 (14)	0.0014 (13)	0.0058 (15)
C2	0.0429 (14)	0.0350 (16)	0.0646 (18)	0.0079 (12)	0.0082 (12)	−0.0045 (14)
C3	0.0343 (12)	0.0313 (15)	0.0397 (15)	−0.0006 (10)	0.0107 (10)	0.0004 (12)
C4	0.0247 (11)	0.0325 (15)	0.0356 (14)	−0.0007 (10)	0.0023 (9)	0.0018 (11)
C5	0.0426 (13)	0.0387 (16)	0.0396 (15)	−0.0083 (12)	0.0064 (10)	0.0103 (13)
C6	0.0446 (14)	0.0321 (16)	0.0540 (17)	−0.0119 (12)	0.0059 (11)	0.0012 (14)
C7	0.0433 (14)	0.0356 (16)	0.0362 (15)	−0.0025 (11)	0.0028 (10)	−0.0070 (13)
C8	0.0377 (13)	0.0527 (19)	0.0494 (17)	−0.0031 (12)	−0.0083 (11)	−0.0073 (14)
C9	0.0698 (18)	0.049 (2)	0.0551 (19)	−0.0046 (15)	0.0030 (14)	−0.0151 (16)
C10	0.0614 (16)	0.0407 (18)	0.0467 (17)	−0.0006 (13)	0.0242 (13)	0.0000 (14)
C11	0.0270 (12)	0.0370 (16)	0.0320 (14)	−0.0064 (11)	0.0064 (9)	−0.0031 (11)
C12	0.0338 (13)	0.0377 (17)	0.0558 (17)	−0.0037 (11)	0.0081 (11)	−0.0057 (13)
O1A	0.0206 (8)	0.0514 (12)	0.0522 (11)	0.0030 (7)	0.0057 (7)	0.0043 (9)
N1A	0.0180 (10)	0.0332 (13)	0.0384 (12)	−0.0016 (9)	0.0056 (7)	0.0044 (9)
C1A	0.0579 (17)	0.045 (2)	0.084 (2)	−0.0083 (14)	0.0174 (15)	−0.0010 (17)
C2A	0.0414 (14)	0.0380 (17)	0.078 (2)	−0.0099 (12)	0.0102 (13)	0.0029 (15)
C3A	0.0366 (13)	0.0381 (16)	0.0450 (16)	−0.0065 (11)	0.0084 (10)	−0.0007 (13)
C4A	0.0249 (11)	0.0332 (15)	0.0437 (15)	−0.0044 (10)	0.0001 (9)	−0.0020 (12)
C5A	0.0415 (14)	0.0390 (17)	0.0590 (18)	−0.0028 (12)	0.0089 (12)	−0.0067 (14)
C6A	0.0408 (15)	0.0461 (19)	0.085 (2)	0.0059 (13)	0.0128 (13)	0.0081 (18)
C7A	0.0384 (13)	0.0450 (17)	0.0410 (15)	−0.0032 (12)	0.0016 (10)	0.0135 (14)
C8A	0.0400 (14)	0.064 (2)	0.0507 (17)	−0.0095 (14)	−0.0097 (11)	0.0142 (16)
C9A	0.079 (2)	0.091 (3)	0.072 (2)	−0.009 (2)	−0.0030 (17)	0.040 (2)
C10A	0.0528 (15)	0.0471 (19)	0.0481 (16)	−0.0036 (13)	0.0164 (12)	0.0013 (14)
C11A	0.0262 (12)	0.0401 (16)	0.0324 (14)	−0.0002 (11)	0.0065 (9)	0.0024 (12)
C12A	0.0390 (14)	0.0480 (19)	0.086 (2)	0.0008 (13)	0.0093 (13)	0.0232 (17)

Geometric parameters (Å, º) top

O1—C11	1.237 (2)	O1A—C11A	1.236 (2)
N1—C11	1.338 (3)	N1A—C11A	1.334 (3)
N1—C4	1.451 (3)	N1A—C4A	1.452 (3)
N1—H1N	0.85 (2)	N1A—H1AN	0.87 (2)
C1—C6	1.536 (3)	C1A—C6A	1.529 (4)
C1—C2	1.547 (4)	C1A—C2A	1.529 (4)
C1—H1A	0.9900	C1A—H1A1	0.9900
C1—H1B	0.9900	C1A—H1A2	0.9900
C2—C3	1.539 (3)	C2A—C3A	1.552 (3)
C2—H2A	0.9900	C2A—H2A1	0.9900
C2—H2B	0.9900	C2A—H2A2	0.9900
C3—C10	1.508 (3)	C3A—C10A	1.494 (3)
C3—C4	1.550 (3)	C3A—C4A	1.536 (3)
C3—C7	1.556 (3)	C3A—C7A	1.560 (3)
C4—C5	1.557 (3)	C4A—C5A	1.588 (3)
C4—H4	1.0000	C4A—H4A	1.0000
C5—C6	1.528 (4)	C5A—C6A	1.523 (4)
C5—H5A	0.9900	C5A—H5A1	0.9900
C5—H5B	0.9900	C5A—H5A2	0.9900
C6—C7	1.541 (4)	C6A—C7A	1.542 (4)
C6—H6	1.0000	C6A—H6A	1.0000
C7—C8	1.534 (3)	C7A—C8A	1.530 (3)
C7—C9	1.537 (4)	C7A—C9A	1.543 (4)
C8—H8A	0.9800	C8A—H8A1	0.9800
C8—H8B	0.9800	C8A—H8A2	0.9800
C8—H8C	0.9800	C8A—H8A3	0.9800
C9—H9A	0.9800	C9A—H9A1	0.9800
C9—H9B	0.9800	C9A—H9A2	0.9800
C9—H9C	0.9800	C9A—H9A3	0.9800
C10—H10D	0.9800	C10A—H10A	0.9800
C10—H10E	0.9800	C10A—H10B	0.9800
C10—H10F	0.9800	C10A—H10C	0.9800
C11—C12	1.500 (3)	C11A—C12A	1.497 (3)
C12—H12A	0.9800	C12A—H12D	0.9800
C12—H12B	0.9800	C12A—H12E	0.9800
C12—H12C	0.9800	C12A—H12F	0.9800

C11—N1—C4	122.38 (18)	C11A—N1A—C4A	123.40 (18)
C11—N1—H1N	117.6 (16)	C11A—N1A—H1AN	119.6 (16)
C4—N1—H1N	119.6 (16)	C4A—N1A—H1AN	116.4 (16)
C6—C1—C2	102.5 (2)	C6A—C1A—C2A	102.8 (2)
C6—C1—H1A	111.3	C6A—C1A—H1A1	111.2
C2—C1—H1A	111.3	C2A—C1A—H1A1	111.2
C6—C1—H1B	111.3	C6A—C1A—H1A2	111.2
C2—C1—H1B	111.3	C2A—C1A—H1A2	111.2
H1A—C1—H1B	109.2	H1A1—C1A—H1A2	109.1
C3—C2—C1	104.02 (18)	C1A—C2A—C3A	103.87 (19)
C3—C2—H2A	111.0	C1A—C2A—H2A1	111.0
C1—C2—H2A	111.0	C3A—C2A—H2A1	111.0
C3—C2—H2B	111.0	C1A—C2A—H2A2	111.0
C1—C2—H2B	111.0	C3A—C2A—H2A2	111.0
H2A—C2—H2B	109.0	H2A1—C2A—H2A2	109.0
C10—C3—C2	114.18 (18)	C10A—C3A—C4A	114.5 (2)
C10—C3—C4	114.7 (2)	C10A—C3A—C2A	113.63 (19)
C2—C3—C4	104.27 (19)	C4A—C3A—C2A	104.2 (2)
C10—C3—C7	117.3 (2)	C10A—C3A—C7A	117.7 (2)
C2—C3—C7	100.96 (19)	C4A—C3A—C7A	103.72 (17)
C4—C3—C7	103.54 (16)	C2A—C3A—C7A	101.3 (2)
N1—C4—C3	116.15 (19)	N1A—C4A—C3A	117.1 (2)
N1—C4—C5	112.55 (17)	N1A—C4A—C5A	110.91 (17)
C3—C4—C5	103.13 (18)	C3A—C4A—C5A	103.01 (19)
N1—C4—H4	108.2	N1A—C4A—H4A	108.5
C3—C4—H4	108.2	C3A—C4A—H4A	108.5
C5—C4—H4	108.2	C5A—C4A—H4A	108.5
C6—C5—C4	102.74 (18)	C6A—C5A—C4A	101.5 (2)
C6—C5—H5A	111.2	C6A—C5A—H5A1	111.5
C4—C5—H5A	111.2	C4A—C5A—H5A1	111.5
C6—C5—H5B	111.2	C6A—C5A—H5A2	111.5
C4—C5—H5B	111.2	C4A—C5A—H5A2	111.5
H5A—C5—H5B	109.1	H5A1—C5A—H5A2	109.3
C5—C6—C1	107.8 (2)	C5A—C6A—C1A	107.5 (2)
C5—C6—C7	102.8 (2)	C5A—C6A—C7A	103.5 (2)
C1—C6—C7	102.75 (19)	C1A—C6A—C7A	103.8 (2)
C5—C6—H6	114.1	C5A—C6A—H6A	113.7
C1—C6—H6	114.1	C1A—C6A—H6A	113.7
C7—C6—H6	114.1	C7A—C6A—H6A	113.7
C8—C7—C9	106.4 (2)	C8A—C7A—C6A	115.7 (2)
C8—C7—C6	114.5 (2)	C8A—C7A—C9A	106.6 (2)
C9—C7—C6	113.5 (2)	C6A—C7A—C9A	113.4 (3)
C8—C7—C3	114.9 (2)	C8A—C7A—C3A	115.1 (2)
C9—C7—C3	114.28 (19)	C6A—C7A—C3A	92.51 (19)
C6—C7—C3	93.26 (18)	C9A—C7A—C3A	113.3 (2)
C7—C8—H8A	109.5	C7A—C8A—H8A1	109.5
C7—C8—H8B	109.5	C7A—C8A—H8A2	109.5
H8A—C8—H8B	109.5	H8A1—C8A—H8A2	109.5
C7—C8—H8C	109.5	C7A—C8A—H8A3	109.5
H8A—C8—H8C	109.5	H8A1—C8A—H8A3	109.5
H8B—C8—H8C	109.5	H8A2—C8A—H8A3	109.5
C7—C9—H9A	109.5	C7A—C9A—H9A1	109.5
C7—C9—H9B	109.5	C7A—C9A—H9A2	109.5
H9A—C9—H9B	109.5	H9A1—C9A—H9A2	109.5
C7—C9—H9C	109.5	C7A—C9A—H9A3	109.5
H9A—C9—H9C	109.5	H9A1—C9A—H9A3	109.5
H9B—C9—H9C	109.5	H9A2—C9A—H9A3	109.5
C3—C10—H10D	109.5	C3A—C10A—H10A	109.5
C3—C10—H10E	109.5	C3A—C10A—H10B	109.5
H10D—C10—H10E	109.5	H10A—C10A—H10B	109.5
C3—C10—H10F	109.5	C3A—C10A—H10C	109.5
H10D—C10—H10F	109.5	H10A—C10A—H10C	109.5
H10E—C10—H10F	109.5	H10B—C10A—H10C	109.5
O1—C11—N1	122.0 (2)	O1A—C11A—N1A	122.7 (2)
O1—C11—C12	121.4 (2)	O1A—C11A—C12A	121.1 (2)
N1—C11—C12	116.64 (18)	N1A—C11A—C12A	116.19 (19)
C11—C12—H12A	109.5	C11A—C12A—H12D	109.5
C11—C12—H12B	109.5	C11A—C12A—H12E	109.5
H12A—C12—H12B	109.5	H12D—C12A—H12E	109.5
C11—C12—H12C	109.5	C11A—C12A—H12F	109.5
H12A—C12—H12C	109.5	H12D—C12A—H12F	109.5
H12B—C12—H12C	109.5	H12E—C12A—H12F	109.5

C6—C1—C2—C3	−1.4 (3)	C6A—C1A—C2A—C3A	−1.5 (3)
C1—C2—C3—C10	163.3 (2)	C1A—C2A—C3A—C10A	163.7 (2)
C1—C2—C3—C4	−70.7 (2)	C1A—C2A—C3A—C4A	−71.1 (2)
C1—C2—C3—C7	36.5 (2)	C1A—C2A—C3A—C7A	36.4 (3)
C11—N1—C4—C3	91.9 (2)	C11A—N1A—C4A—C3A	91.2 (3)
C11—N1—C4—C5	−149.5 (2)	C11A—N1A—C4A—C5A	−151.0 (2)
C10—C3—C4—N1	−35.4 (3)	C10A—C3A—C4A—N1A	−38.7 (3)
C2—C3—C4—N1	−161.05 (18)	C2A—C3A—C4A—N1A	−163.36 (18)
C7—C3—C4—N1	93.7 (2)	C7A—C3A—C4A—N1A	91.0 (2)
C10—C3—C4—C5	−159.00 (19)	C10A—C3A—C4A—C5A	−160.7 (2)
C2—C3—C4—C5	75.4 (2)	C2A—C3A—C4A—C5A	74.6 (2)
C7—C3—C4—C5	−29.9 (2)	C7A—C3A—C4A—C5A	−31.1 (2)
N1—C4—C5—C6	−131.5 (2)	N1A—C4A—C5A—C6A	−131.0 (2)
C3—C4—C5—C6	−5.6 (2)	C3A—C4A—C5A—C6A	−4.9 (2)
C4—C5—C6—C1	−68.3 (2)	C4A—C5A—C6A—C1A	−69.5 (3)
C4—C5—C6—C7	39.7 (2)	C4A—C5A—C6A—C7A	39.9 (2)
C2—C1—C6—C5	73.3 (2)	C2A—C1A—C6A—C5A	74.5 (3)
C2—C1—C6—C7	−34.8 (3)	C2A—C1A—C6A—C7A	−34.7 (3)
C5—C6—C7—C8	63.2 (2)	C5A—C6A—C7A—C8A	62.4 (3)
C1—C6—C7—C8	175.1 (2)	C1A—C6A—C7A—C8A	174.6 (2)
C5—C6—C7—C9	−174.4 (2)	C5A—C6A—C7A—C9A	−173.9 (2)
C1—C6—C7—C9	−62.5 (3)	C1A—C6A—C7A—C9A	−61.7 (3)
C5—C6—C7—C3	−56.1 (2)	C5A—C6A—C7A—C3A	−57.1 (2)
C1—C6—C7—C3	55.8 (2)	C1A—C6A—C7A—C3A	55.1 (2)
C10—C3—C7—C8	60.6 (3)	C10A—C3A—C7A—C8A	60.7 (3)
C2—C3—C7—C8	−174.6 (2)	C4A—C3A—C7A—C8A	−66.9 (3)
C4—C3—C7—C8	−66.9 (2)	C2A—C3A—C7A—C8A	−174.8 (2)
C10—C3—C7—C9	−62.8 (3)	C10A—C3A—C7A—C6A	−179.3 (2)
C2—C3—C7—C9	62.0 (3)	C4A—C3A—C7A—C6A	53.1 (2)
C4—C3—C7—C9	169.7 (2)	C2A—C3A—C7A—C6A	−54.7 (2)
C10—C3—C7—C6	179.6 (2)	C10A—C3A—C7A—C9A	−62.4 (3)
C2—C3—C7—C6	−55.7 (2)	C4A—C3A—C7A—C9A	170.0 (2)
C4—C3—C7—C6	52.0 (2)	C2A—C3A—C7A—C9A	62.1 (3)
C4—N1—C11—O1	−1.1 (3)	C4A—N1A—C11A—O1A	−4.6 (3)
C4—N1—C11—C12	179.1 (2)	C4A—N1A—C11A—C12A	176.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1Aⁱ	0.85 (2)	2.06 (2)	2.900 (2)	170 (2)
N1A—H1AN···O1ⁱⁱ	0.87 (2)	2.03 (2)	2.886 (2)	172 (2)
C8A—H8A1···O1ⁱⁱ	0.98	2.57	3.524 (3)	165
C12—H12C···O1ⁱⁱ	0.98	2.52	3.468 (3)	164

Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z.

(2) (±)-2-Chloro-N-[(1RS,2RS,4RS)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl]acetamide top

Crystal data top

C₁₂H₂₀ClNO	F(000) = 992
M_r = 229.74	D_x = 1.234 Mg m⁻³
Orthorhombic, Pcab	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2bc 2ac	Cell parameters from 24915 reflections
a = 9.6852 (2) Å	θ = 1.0–30.0°
b = 10.7589 (3) Å	µ = 0.28 mm⁻¹
c = 23.7261 (8) Å	T = 173 K
V = 2472.31 (12) Å³	Plate, colorless
Z = 8	0.35 × 0.10 × 0.09 mm

Data collection top

Nonius KappaCCD diffractometer	1854 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.097
Graphite monochromator	θ_max = 30.0°, θ_min = 2.6°
φ and ω scan	h = −13→13
6757 measured reflections	k = −15→15
3611 independent reflections	l = −33→33

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0497P)² + 1.7639P] where P = (F_o² + 2F_c²)/3
3611 reflections	(Δ/σ)_max < 0.001
143 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₂H₂₀ClNO	V = 2472.31 (12) Å³
M_r = 229.74	Z = 8
Orthorhombic, Pcab	Mo Kα radiation
a = 9.6852 (2) Å	µ = 0.28 mm⁻¹
b = 10.7589 (3) Å	T = 173 K
c = 23.7261 (8) Å	0.35 × 0.10 × 0.09 mm

Data collection top

Nonius KappaCCD diffractometer	1854 reflections with I > 2σ(I)
6757 measured reflections	R_int = 0.097
3611 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	0 restraints
wR(F²) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.51 e Å⁻³
3611 reflections	Δρ_min = −0.38 e Å⁻³
143 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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
Cl1	0.83924 (7)	1.01572 (7)	0.43765 (4)	0.0460 (3)
O1	0.68852 (15)	0.76668 (17)	0.44335 (8)	0.0326 (5)
N1	0.8914 (2)	0.6671 (2)	0.42922 (10)	0.0241 (5)
H1	0.972 (3)	0.673 (2)	0.4329 (11)	0.026 (8)*
C1	0.7790 (3)	0.3051 (3)	0.36991 (15)	0.0436 (8)
H1A	0.7757	0.2399	0.3417	0.052*
H1B	0.7467	0.2723	0.4056	0.052*
C2	0.6933 (3)	0.4183 (3)	0.35161 (14)	0.0377 (7)
H2A	0.6194	0.4345	0.3782	0.045*
H2B	0.6539	0.4055	0.3145	0.045*
C3	0.7980 (2)	0.5264 (2)	0.35096 (12)	0.0292 (6)
C4	0.8313 (2)	0.5475 (2)	0.41407 (11)	0.0260 (6)
H4	0.7456	0.5373	0.4355	0.031*
C5	0.9296 (3)	0.4360 (2)	0.42903 (13)	0.0332 (7)
H5A	1.0224	0.4647	0.4373	0.040*
H5B	0.8950	0.3891	0.4609	0.040*
C6	0.9261 (3)	0.3591 (3)	0.37543 (15)	0.0409 (8)
H6	0.9999	0.2970	0.3727	0.049*
C7	0.9285 (3)	0.4580 (3)	0.32796 (12)	0.0321 (7)
C8	1.0598 (3)	0.5389 (3)	0.32675 (14)	0.0435 (8)
H8A	1.1362	0.4900	0.3136	0.065*
H8B	1.0792	0.5688	0.3640	0.065*
H8C	1.0458	0.6082	0.3019	0.065*
C9	0.9126 (4)	0.4040 (4)	0.26906 (16)	0.0626 (11)
H9A	0.9126	0.4701	0.2419	0.094*
H9B	0.8271	0.3592	0.2667	0.094*
H9C	0.9880	0.3486	0.2614	0.094*
C10	0.7496 (3)	0.6398 (3)	0.31989 (14)	0.0427 (8)
H10A	0.7357	0.6197	0.2809	0.064*
H10B	0.8179	0.7042	0.3230	0.064*
H10C	0.6642	0.6682	0.3359	0.064*
C11	0.8159 (2)	0.7647 (2)	0.44464 (11)	0.0239 (6)
C12	0.8982 (2)	0.8735 (2)	0.46654 (14)	0.0324 (7)
H12A	0.9947	0.8620	0.4571	0.039*
H12B	0.8906	0.8767	0.5073	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0364 (4)	0.0305 (4)	0.0711 (6)	−0.0062 (3)	−0.0118 (4)	0.0006 (4)
O1	0.0136 (8)	0.0345 (10)	0.0499 (13)	0.0001 (7)	−0.0002 (8)	−0.0073 (10)
N1	0.0120 (10)	0.0280 (11)	0.0323 (14)	−0.0021 (8)	−0.0006 (9)	−0.0028 (10)
C1	0.0349 (15)	0.0323 (15)	0.063 (2)	−0.0059 (12)	−0.0009 (15)	−0.0040 (16)
C2	0.0213 (13)	0.0361 (16)	0.056 (2)	−0.0064 (11)	0.0011 (12)	−0.0065 (15)
C3	0.0238 (12)	0.0276 (14)	0.0363 (17)	−0.0023 (10)	−0.0014 (11)	−0.0005 (13)
C4	0.0203 (12)	0.0248 (13)	0.0329 (16)	−0.0026 (10)	0.0057 (11)	0.0000 (11)
C5	0.0273 (13)	0.0285 (13)	0.0439 (18)	0.0001 (11)	0.0000 (12)	0.0083 (14)
C6	0.0261 (14)	0.0277 (15)	0.069 (2)	0.0058 (11)	−0.0011 (14)	−0.0065 (15)
C7	0.0247 (13)	0.0378 (16)	0.0338 (17)	−0.0059 (11)	0.0055 (11)	−0.0111 (14)
C8	0.0324 (15)	0.054 (2)	0.0442 (19)	−0.0137 (14)	0.0148 (14)	−0.0130 (16)
C9	0.0484 (19)	0.078 (3)	0.062 (3)	−0.0176 (18)	0.0151 (17)	−0.035 (2)
C10	0.0449 (17)	0.0419 (17)	0.0412 (19)	0.0003 (15)	−0.0156 (14)	−0.0008 (15)
C11	0.0161 (11)	0.0268 (13)	0.0289 (15)	−0.0006 (9)	−0.0008 (10)	−0.0028 (12)
C12	0.0180 (12)	0.0304 (14)	0.0488 (19)	0.0023 (10)	−0.0066 (12)	−0.0108 (14)

Geometric parameters (Å, º) top

Cl1—C12	1.771 (3)	C5—H5A	0.9700
O1—C11	1.235 (3)	C5—H5B	0.9700
N1—C11	1.331 (3)	C6—C7	1.550 (4)
N1—C4	1.457 (3)	C6—H6	0.9800
N1—H1	0.78 (3)	C7—C9	1.522 (4)
C1—C2	1.536 (4)	C7—C8	1.541 (4)
C1—C6	1.544 (4)	C8—H8A	0.9600
C1—H1A	0.9700	C8—H8B	0.9600
C1—H1B	0.9700	C8—H8C	0.9600
C2—C3	1.543 (4)	C9—H9A	0.9600
C2—H2A	0.9700	C9—H9B	0.9600
C2—H2B	0.9700	C9—H9C	0.9600
C3—C10	1.501 (4)	C10—H10A	0.9600
C3—C4	1.548 (4)	C10—H10B	0.9600
C3—C7	1.561 (4)	C10—H10C	0.9600
C4—C5	1.573 (4)	C11—C12	1.508 (3)
C4—H4	0.9800	C12—H12A	0.9700
C5—C6	1.517 (4)	C12—H12B	0.9700

C11—N1—C4	123.0 (2)	C5—C6—H6	114.2
C11—N1—H1	117 (2)	C1—C6—H6	114.2
C4—N1—H1	119 (2)	C7—C6—H6	114.2
C2—C1—C6	102.9 (2)	C9—C7—C8	106.4 (2)
C2—C1—H1A	111.2	C9—C7—C6	113.8 (3)
C6—C1—H1A	111.2	C8—C7—C6	114.4 (2)
C2—C1—H1B	111.2	C9—C7—C3	114.8 (2)
C6—C1—H1B	111.2	C8—C7—C3	114.1 (2)
H1A—C1—H1B	109.1	C6—C7—C3	93.3 (2)
C1—C2—C3	104.2 (2)	C7—C8—H8A	109.5
C1—C2—H2A	110.9	C7—C8—H8B	109.5
C3—C2—H2A	110.9	H8A—C8—H8B	109.5
C1—C2—H2B	110.9	C7—C8—H8C	109.5
C3—C2—H2B	110.9	H8A—C8—H8C	109.5
H2A—C2—H2B	108.9	H8B—C8—H8C	109.5
C10—C3—C2	114.3 (2)	C7—C9—H9A	109.5
C10—C3—C4	114.9 (2)	C7—C9—H9B	109.5
C2—C3—C4	103.7 (2)	H9A—C9—H9B	109.5
C10—C3—C7	117.7 (2)	C7—C9—H9C	109.5
C2—C3—C7	100.4 (2)	H9A—C9—H9C	109.5
C4—C3—C7	103.8 (2)	H9B—C9—H9C	109.5
N1—C4—C3	116.8 (2)	C3—C10—H10A	109.5
N1—C4—C5	112.1 (2)	C3—C10—H10B	109.5
C3—C4—C5	103.4 (2)	H10A—C10—H10B	109.5
N1—C4—H4	108.0	C3—C10—H10C	109.5
C3—C4—H4	108.0	H10A—C10—H10C	109.5
C5—C4—H4	108.0	H10B—C10—H10C	109.5
C6—C5—C4	102.3 (2)	O1—C11—N1	123.8 (2)
C6—C5—H5A	111.3	O1—C11—C12	121.5 (2)
C4—C5—H5A	111.3	N1—C11—C12	114.63 (19)
C6—C5—H5B	111.3	C11—C12—Cl1	111.55 (18)
C4—C5—H5B	111.3	C11—C12—H12A	109.3
H5A—C5—H5B	109.2	Cl1—C12—H12A	109.3
C5—C6—C1	107.3 (2)	C11—C12—H12B	109.3
C5—C6—C7	103.6 (2)	Cl1—C12—H12B	109.3
C1—C6—C7	102.1 (2)	H12A—C12—H12B	108.0

C6—C1—C2—C3	−2.3 (3)	C1—C6—C7—C9	−63.4 (3)
C1—C2—C3—C10	164.5 (3)	C5—C6—C7—C8	62.6 (3)
C1—C2—C3—C4	−69.6 (3)	C1—C6—C7—C8	174.0 (2)
C1—C2—C3—C7	37.5 (3)	C5—C6—C7—C3	−55.8 (2)
C11—N1—C4—C3	91.6 (3)	C1—C6—C7—C3	55.6 (2)
C11—N1—C4—C5	−149.3 (2)	C10—C3—C7—C9	−62.8 (3)
C10—C3—C4—N1	−35.2 (3)	C2—C3—C7—C9	61.9 (3)
C2—C3—C4—N1	−160.7 (2)	C4—C3—C7—C9	168.9 (2)
C7—C3—C4—N1	94.7 (2)	C10—C3—C7—C8	60.3 (3)
C10—C3—C4—C5	−158.8 (2)	C2—C3—C7—C8	−175.0 (3)
C2—C3—C4—C5	75.6 (2)	C4—C3—C7—C8	−67.9 (3)
C7—C3—C4—C5	−28.9 (2)	C10—C3—C7—C6	179.0 (2)
N1—C4—C5—C6	−132.9 (2)	C2—C3—C7—C6	−56.3 (2)
C3—C4—C5—C6	−6.2 (2)	C4—C3—C7—C6	50.8 (2)
C4—C5—C6—C1	−67.7 (3)	C4—N1—C11—O1	−6.0 (4)
C4—C5—C6—C7	39.8 (2)	C4—N1—C11—C12	171.7 (2)
C2—C1—C6—C5	74.5 (3)	O1—C11—C12—Cl1	−47.2 (3)
C2—C1—C6—C7	−34.1 (3)	N1—C11—C12—Cl1	135.1 (2)
C5—C6—C7—C9	−174.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.79 (3)	2.21 (3)	2.983 (2)	168 (2)
C12—H12A···O1ⁱ	0.97	2.36	3.238 (3)	151

Symmetry code: (i) x+1/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º) for (1) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1Aⁱ	0.85 (2)	2.06 (2)	2.900 (2)	170 (2)
N1A—H1AN···O1ⁱⁱ	0.87 (2)	2.03 (2)	2.886 (2)	172 (2)
C8A—H8A1···O1ⁱⁱ	0.98	2.57	3.524 (3)	165
C12—H12C···O1ⁱⁱ	0.98	2.52	3.468 (3)	164

Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y, −z.

Hydrogen-bond geometry (Å, º) for (2) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.79 (3)	2.21 (3)	2.983 (2)	168 (2)
C12—H12A···O1ⁱ	0.97	2.36	3.238 (3)	151

Symmetry code: (i) x+1/2, −y+3/2, z.

Experimental details

	(1)	(2)
Crystal data
Chemical formula	C₁₂H₂₁NO	C₁₂H₂₀ClNO
M_r	195.30	229.74
Crystal system, space group	Monoclinic, P2₁/n	Orthorhombic, Pcab
Temperature (K)	173	173
a, b, c (Å)	9.6820 (6), 10.6540 (3), 23.3676 (7)	9.6852 (2), 10.7589 (3), 23.7261 (8)
α, β, γ (°)	90, 97.184 (10), 90	90, 90, 90
V (Å³)	2391.49 (19)	2472.31 (12)
Z	8	8
Radiation type	Mo Kα	Mo Kα
µ (mm⁻¹)	0.07	0.28
Crystal size (mm)	0.18 × 0.12 × 0.09	0.35 × 0.10 × 0.09

Data collection
Diffractometer	Nonius KappaCCD diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7908, 4320, 2637	6757, 3611, 1854
R_int	0.056	0.097
(sin θ/λ)_max (Å⁻¹)	0.600	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.159, 1.05	0.073, 0.160, 1.02
No. of reflections	4320	3611
No. of parameters	269	143
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.20	0.51, −0.38

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR2011 (Burla et al., 2012), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

This work was financed by the Latvian Council of Science (grant No 12.0291). DP thanks the JSC `Olainfarm' for a scholarship. JSC `Grindeks' is acknowledged for the donation of organic solvents.

References

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Mallamo, M., Mazzone, A., Polidori, G. & Spagna, R. (2012). J. Appl. Cryst. 45, 357–361. Web of Science CrossRef CAS IUCr Journals Google Scholar
Chelucci, G. (2006). Chem. Soc. Rev. 35, 1230–1243. CrossRef PubMed CAS Google Scholar
Duclos, R. I. Jr, Lu, D., Guo, J. & Makriyannis, A. (2008). Tetrahedron Lett. 49, 5587–5589. CrossRef CAS PubMed Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662–671. Web of Science CSD CrossRef CAS Google Scholar
Hanzawa, Y., Kasashima, Y., Tomono, K., Mino, T., Sakamoto, M. & Fujita, T. (2012). J. Oleo Sci. 61, 391–399. Google Scholar
Horváthová, E., Kozics, K., Srančíková, A., Hunáková, Ĺ., Gálová, E., Ševčovičová, A. & Slameňová, D. (2012). Mutagenesis, 27, 581–588. PubMed Google Scholar
Jiang, D., He, T., Ma, L. & Wang, Z. (2014). RSC Adv. 4, 64936–64946. CrossRef CAS Google Scholar
Langlois, Y. & Kouklovsky, C. (2009). Synlett, pp. 3065–3081. CrossRef Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Nonius (1997). KappaCCD Server Software. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Prusinowska, N., Bendzińska-Berus, W., Jelecki, M., Rychlewska, U. & Kwit, M. (2015). Eur. J. Org. Chem. 2015, 738–749. CSD CrossRef CAS Google Scholar
Ramón, D. J. & Yus, M. (2007). Synlett, pp. 2309–2320. Google Scholar
Schenone, S., Bruno, O., Ranise, A., Bondavalli, F., Filippelli, W., Falcone, G. & Rinaldi, B. (2000). Farmaco, 55, 495–498. CrossRef PubMed CAS Google Scholar
Seebaluck, R., Gurib-Fakim, A. & Mahomoodally, F. (2015). J. Ethnopharmacol. 159, 137–157. CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stavrakov, G., Philipova, I., Valcheva, V. & Momekov, G. (2014a). Bioorg. Med. Chem. Lett. 24, 165–167. CrossRef CAS PubMed Google Scholar
Stavrakov, G., Valcheva, V., Philipova, I. & Doytchinova, I. (2014b). J. Mol. Graph. Model. 51, 7–12. CrossRef CAS PubMed Google Scholar
Steinbrecher, T., Hrenn, A., Dormann, K. L., Merfort, I. & Labahn, A. (2008). Bioorg. Med. Chem. 16, 2385–2390. CrossRef PubMed CAS Google Scholar
Turks, M., Strakova, I., Gorovojs, K., Belyakov, S., Piven, Y., Khlebnicova, T. S. & Lakhvich, F. (2012). Tetrahedron, 68, 6131–6140. CSD CrossRef CAS Google Scholar
Ung, A. T., Williams, S. G., Angeloski, A., Ashmore, J., Kuzhiumparambil, U., Bhadbhade, M. & Bishop, R. (2014). Monatsh. Chem. 145, 983–992. CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 71| Part 10| October 2015| Pages 1117-1120

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