3,5-Dibromo-4-oxo-2,2,6,6-tetra­methyl­piperidin-1-yl oxide

Zhu, G.-Z.; Xu, S.-P.; Li, C.-Y.

doi:10.1107/S1600536811046812

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page o3262

https://doi.org/10.1107/S1600536811046812

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3,5-Dibromo-4-oxo-2,2,6,6-tetramethylpiperidin-1-yl oxide

Guang-Zhou Zhu,^a Suo-Ping Xu ^a ^* and Cui-Yun Li ^b ^*

^aJiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Xuzhou Normal University, Xuzhou 221116, People's Repulic of China, and ^bState Key Laboratory of Pharmaceutical Biotechnology, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: benbenshell@yahoo.com.cn, licuiyun0909@yahoo.cn

(Received 12 October 2011; accepted 7 November 2011; online 12 November 2011)

In the title compound, C₉H₁₄Br₂NO₂, the substituted ring exhibits a chair conformation. A crystallographic mirror plane, passing through the N atom, the O atoms and the C atom in the 4-position, bisects the molecule.

Related literature

For medical applications of similar compounds, see: Aubert et al. (2011 ); Brike (1990 ); Xu et al. (2009 ). For puckering parameters see: Cremer & Pople(1975 ).

Experimental

Crystal data

C₉H₁₄Br₂NO₂
M_r = 328.03
Orthorhombic, P n m a
a = 11.6745 (9) Å
b = 16.0848 (14) Å
c = 5.9301 (4) Å
V = 1113.57 (15) Å³
Z = 4
Mo Kα radiation
μ = 7.26 mm⁻¹
T = 298 K
0.45 × 0.42 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.139, T_max = 0.355
5193 measured reflections
1018 independent reflections
774 reflections with I > 2σ(I)
R_int = 0.118

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.089
S = 1.04
1018 reflections
72 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811046812/bx2376sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046812/bx2376Isup2.hkl

checkCIF report

Comment top

3,5-dibromo-4-oxo-2,2,6,6-tetramethylpiperidin-1-yl oxide is an important intermediate medicament. It is synthesized in a wide range of medical applications (Aubert et al. (2011); Brike (1990); Xu et al. (2009)). The complete molecule of the title compound, C₉H₁₄Br₂NO₂, is generated by crystallographic mirror symmetry, with two O, one C in the 3-position and one N atom lying on the mirror plane, Fig1. The substituted cyclohexyl ring adopts a chair conformation ( Q_T=0.562 (4)Å, θ =19.0 (4)°, φ =180.0 (12)° ), Cremer & Pople, (1975)

Related literature top

For medical applications of similar compounds, see: Aubert et al. (2011); Brike (1990); Xu et al. (2009). For puckering parameters see: Cremer & Pople(1975).

Experimental top

The title compound was synthetized by reaction between 4-Oxo-2,2,6,6-tetramethylpiperidin-1-yl oxide (2 mmol) and bromine (2 mmol), dissolved in CH₂CH₂Cl₂ and mixed together for 2 h. Large block crystals were precipitated, filtered ,washed with ethanol and dried in air (yield 80%).

Structure description top

For medical applications of similar compounds, see: Aubert et al. (2011); Brike (1990); Xu et al. (2009). For puckering parameters see: Cremer & Pople(1975).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids.

3,5-Dibromo-4-oxo-2,2,6,6-tetramethylpiperidin-1-yl oxide top

Crystal data top

C₉H₁₄Br₂NO₂	D_x = 1.957 Mg m⁻³
M_r = 328.03	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1704 reflections
a = 11.6745 (9) Å	θ = 3.5–26.6°
b = 16.0848 (14) Å	µ = 7.26 mm⁻¹
c = 5.9301 (4) Å	T = 298 K
V = 1113.57 (15) Å³	Block, orange
Z = 4	0.45 × 0.42 × 0.18 mm
F(000) = 644

Data collection top

Bruker SMART CCD area-detector diffractometer	1018 independent reflections
Radiation source: fine-focus sealed tube	774 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.118
phi and ω scans	θ_max = 25.0°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→12
T_min = 0.139, T_max = 0.355	k = −19→18
5193 measured reflections	l = −6→7

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0364P)²] where P = (F_o² + 2F_c²)/3
1018 reflections	(Δ/σ)_max < 0.001
72 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

C₉H₁₄Br₂NO₂	V = 1113.57 (15) Å³
M_r = 328.03	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 11.6745 (9) Å	µ = 7.26 mm⁻¹
b = 16.0848 (14) Å	T = 298 K
c = 5.9301 (4) Å	0.45 × 0.42 × 0.18 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1018 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	774 reflections with I > 2σ(I)
T_min = 0.139, T_max = 0.355	R_int = 0.118
5193 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.04	Δρ_max = 0.52 e Å⁻³
1018 reflections	Δρ_min = −0.64 e Å⁻³
72 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
Br1	0.28737 (4)	0.42632 (3)	0.59566 (7)	0.0414 (2)
N1	0.4892 (4)	0.2500	0.2492 (7)	0.0268 (11)
O1	0.5770 (4)	0.2500	0.1217 (6)	0.0448 (11)
O2	0.2994 (3)	0.2500	0.7814 (7)	0.0384 (10)
C1	0.4591 (3)	0.3333 (2)	0.3498 (6)	0.0237 (9)
C2	0.3343 (3)	0.3265 (2)	0.4364 (6)	0.0263 (9)
H2	0.2844	0.3206	0.3045	0.032*
C3	0.3177 (4)	0.2500	0.5827 (10)	0.0277 (13)
C4	0.5446 (3)	0.3542 (3)	0.5367 (7)	0.0354 (10)
H4A	0.5310	0.3188	0.6643	0.053*
H4B	0.5354	0.4112	0.5808	0.053*
H4C	0.6212	0.3456	0.4824	0.053*
C5	0.4652 (4)	0.3975 (3)	0.1615 (8)	0.0418 (11)
H5A	0.5425	0.4012	0.1069	0.063*
H5B	0.4416	0.4507	0.2182	0.063*
H5C	0.4155	0.3811	0.0405	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0384 (3)	0.0281 (3)	0.0576 (4)	0.00706 (19)	0.00867 (18)	−0.0047 (2)
N1	0.024 (2)	0.033 (3)	0.023 (3)	0.000	0.0032 (17)	0.000
O1	0.039 (3)	0.050 (3)	0.046 (3)	0.000	0.0234 (19)	0.000
O2	0.048 (3)	0.034 (2)	0.033 (3)	0.000	0.0153 (19)	0.000
C1	0.025 (2)	0.022 (2)	0.024 (2)	−0.0017 (17)	0.0009 (14)	−0.0011 (16)
C2	0.023 (2)	0.024 (2)	0.033 (2)	0.0032 (17)	−0.0028 (14)	−0.0031 (17)
C3	0.011 (3)	0.026 (3)	0.046 (4)	0.000	−0.001 (2)	0.000
C4	0.024 (2)	0.034 (2)	0.047 (3)	−0.001 (2)	−0.0046 (17)	−0.007 (2)
C5	0.053 (3)	0.034 (2)	0.039 (3)	−0.001 (2)	0.006 (2)	0.007 (2)

Geometric parameters (Å, º) top

Br1—C2	1.942 (4)	C2—H2	0.9800
N1—O1	1.274 (5)	C3—C2ⁱ	1.518 (5)
N1—C1ⁱ	1.509 (4)	C4—H4A	0.9600
N1—C1	1.509 (4)	C4—H4B	0.9600
O2—C3	1.198 (6)	C4—H4C	0.9600
C1—C5	1.523 (6)	C5—H5A	0.9600
C1—C4	1.529 (5)	C5—H5B	0.9600
C1—C2	1.548 (5)	C5—H5C	0.9600
C2—C3	1.518 (5)

O1—N1—C1ⁱ	115.0 (2)	O2—C3—C2ⁱ	125.8 (2)
O1—N1—C1	115.0 (2)	O2—C3—C2	125.8 (2)
C1ⁱ—N1—C1	125.3 (4)	C2ⁱ—C3—C2	108.3 (5)
N1—C1—C5	107.5 (3)	C1—C4—H4A	109.5
N1—C1—C4	109.2 (3)	C1—C4—H4B	109.5
C5—C1—C4	110.6 (3)	H4A—C4—H4B	109.5
N1—C1—C2	106.7 (3)	C1—C4—H4C	109.5
C5—C1—C2	109.6 (3)	H4A—C4—H4C	109.5
C4—C1—C2	112.9 (3)	H4B—C4—H4C	109.5
C3—C2—C1	111.5 (3)	C1—C5—H5A	109.5
C3—C2—Br1	110.9 (3)	C1—C5—H5B	109.5
C1—C2—Br1	111.6 (3)	H5A—C5—H5B	109.5
C3—C2—H2	107.5	C1—C5—H5C	109.5
C1—C2—H2	107.5	H5A—C5—H5C	109.5
Br1—C2—H2	107.5	H5B—C5—H5C	109.5

O1—N1—C1—C5	46.0 (5)	C4—C1—C2—C3	−69.8 (4)
C1ⁱ—N1—C1—C5	−159.6 (3)	N1—C1—C2—Br1	174.9 (2)
O1—N1—C1—C4	−74.1 (4)	C5—C1—C2—Br1	−69.0 (3)
C1ⁱ—N1—C1—C4	80.3 (5)	C4—C1—C2—Br1	54.8 (4)
O1—N1—C1—C2	163.5 (4)	C1—C2—C3—O2	111.8 (5)
C1ⁱ—N1—C1—C2	−42.1 (6)	Br1—C2—C3—O2	−13.2 (6)
N1—C1—C2—C3	50.2 (4)	C1—C2—C3—C2ⁱ	−65.4 (5)
C5—C1—C2—C3	166.4 (3)	Br1—C2—C3—C2ⁱ	169.5 (2)

Symmetry code: (i) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₉H₁₄Br₂NO₂
M_r	328.03
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	11.6745 (9), 16.0848 (14), 5.9301 (4)
V (Å³)	1113.57 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.26
Crystal size (mm)	0.45 × 0.42 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.139, 0.355
No. of measured, independent and observed [I > 2σ(I)] reflections	5193, 1018, 774
R_int	0.118
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.089, 1.04
No. of reflections	1018
No. of parameters	72
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.64

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Aubert, M., Wilen, C.-E., Pfaendner, R., Kniesel, S., Hoppe, H. & Roth, M. (2011). Polymer. Degrad. Stabil. 96, 328–333. Web of Science CrossRef CAS Google Scholar
Brike, M. E. (1990). Synth. Commun. 20, 597–601. Google Scholar
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, S.-P., Cheng, K. & Shi, L. (2009). Z. Kristallogr. New Cryst. Struct. 224, 461-462. Google Scholar