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The title compound, C9H19N2O, was studied in the context of nitroxide radicals bearing amino or hydr­oxy groups as candidates for obtaining thin films of mol­ecular magnets by thermal evaporation in high vacuum on various substrates; the knowledge of its crystal structure is useful for checking the nature and quality of the films. In the crystal structure ATEMPO radicals are linked by weak inter­molecular N—H...O hydrogen bonds to form infinite chains running along [010]. Structural features of the radical are similar to those reported for clathrates or adducts involving ATEMPO: the piperidine ring has a chair conformation and the N—O. bond length is 1.2870 (13) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032898/cf2110sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032898/cf2110Isup2.hkl
Contains datablock I

CCDC reference: 657697

Key indicators

  • Single-crystal X-ray study
  • T = 160 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.040
  • wR factor = 0.101
  • Data-to-parameter ratio = 11.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2B ... ?
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The search for molecular magnets derived from nitroxides and composed exclusively of light elements is an active field (Miller & Epstein, 1994). When prepared as oriented thin films of good optical quality, applications are foreseen in magnetic-optics. Thin films of the nitrophenyl nitronyl nitroxide radical have been obtained by thermal evaporation in high vacuum on glass and cleaved NaCl (001) substrates (Caro et al., 1998). Nitroxide radicals bearing amino or hydroxy groups seem good candidates for processing thin films in which molecule-molecule and molecule-substrate interactions would be favoured by hydrogen bonds. In this context we have prepared the 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl radical (ATEMPO) according to a procedure described by Rosen (1974). The knowledge of the crystal structure is useful for checking the nature and the quality of the films. Single crystals of the material were obtained by evaporation of an ethanol solution. The molecular structure of ATEMPO is shown in Figure 1, in the solid state the piperidine ring displays a chair conformation. The N—O. bond length is 1.2870 (13) Å. In the crystal structure ATEMPO radicals are linked by weak intermolecular N—H···O hydrogen bonds to form infinite chains running along [010] (Figure 2). The structural features of the isolated ATEMPO radical are similar to those reported for ATEMPO included in clathrates (Mazaki et al., 1992) or adducts (Boubekeur et al., 2006).

Related literature top

For the synthesis of ATEMPO, see Rosen (1974). For related structures, see Mazaki et al. (1992); Boubekeur et al. (2006). For literature on thin films of molecular magnets, see Miller & Epstein (1994); Caro et al. (1998).

Experimental top

The title compound was prepared according to a previously published procedure (Rosen, 1974). The resulting solid was dissolved in ethanol. Crystals suitable for X-ray structural study were obtained by evaporation of this ethanol solution.

Refinement top

H atoms were clearly located in a difference map. Their positions were refined together with a common Uiso(H) which converged to a value of 0.0529 (11) Å2. C—H distances are in the range 0.95 (2)–1.03 (2) Å, N—H distances are 0.85 (2) and 0.93 (2) Å, the longest being involved in a weak intermolecular N—H···O hydrogen bond.

Structure description top

The search for molecular magnets derived from nitroxides and composed exclusively of light elements is an active field (Miller & Epstein, 1994). When prepared as oriented thin films of good optical quality, applications are foreseen in magnetic-optics. Thin films of the nitrophenyl nitronyl nitroxide radical have been obtained by thermal evaporation in high vacuum on glass and cleaved NaCl (001) substrates (Caro et al., 1998). Nitroxide radicals bearing amino or hydroxy groups seem good candidates for processing thin films in which molecule-molecule and molecule-substrate interactions would be favoured by hydrogen bonds. In this context we have prepared the 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl radical (ATEMPO) according to a procedure described by Rosen (1974). The knowledge of the crystal structure is useful for checking the nature and the quality of the films. Single crystals of the material were obtained by evaporation of an ethanol solution. The molecular structure of ATEMPO is shown in Figure 1, in the solid state the piperidine ring displays a chair conformation. The N—O. bond length is 1.2870 (13) Å. In the crystal structure ATEMPO radicals are linked by weak intermolecular N—H···O hydrogen bonds to form infinite chains running along [010] (Figure 2). The structural features of the isolated ATEMPO radical are similar to those reported for ATEMPO included in clathrates (Mazaki et al., 1992) or adducts (Boubekeur et al., 2006).

For the synthesis of ATEMPO, see Rosen (1974). For related structures, see Mazaki et al. (1992); Boubekeur et al. (2006). For literature on thin films of molecular magnets, see Miller & Epstein (1994); Caro et al. (1998).

Computing details top

Data collection: IPDS (Stoe & Cie, 1996); cell refinement: IPDS; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), CAMERON (Pearce & Watkin, 1993) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of ATEMPO, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The packing of ATEMPO. Hydrogen bonds drawn as dashed lines. H atoms not involved in hydrogen bonding have been omitted.
4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl top
Crystal data top
C9H19N2OF(000) = 380
Mr = 171.26Dx = 1.110 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 943 reflections
a = 5.721 (2) Åθ = 3.1–26.1°
b = 12.919 (3) ŵ = 0.07 mm1
c = 13.955 (4) ÅT = 160 K
β = 96.61 (4)°Block, orange
V = 1024.6 (5) Å30.31 × 0.24 × 0.20 mm
Z = 4
Data collection top
Stoe IPDS imaging plate
diffractometer
1618 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.041
Graphite monochromatorθmax = 26.1°, θmin = 1.7°
φ scans with 1.5° stepsh = 77
7824 measured reflectionsk = 1515
1989 independent reflectionsl = 1617
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: difference Fourier map
wR(F2) = 0.101All H-atom parameters refined
S = 1.04 w = 1/[σ2(Fo2) + (0.0436P)2 + 0.2605P]
where P = (Fo2 + 2Fc2)/3
1989 reflections(Δ/σ)max = 0.001
167 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C9H19N2OV = 1024.6 (5) Å3
Mr = 171.26Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.721 (2) ŵ = 0.07 mm1
b = 12.919 (3) ÅT = 160 K
c = 13.955 (4) Å0.31 × 0.24 × 0.20 mm
β = 96.61 (4)°
Data collection top
Stoe IPDS imaging plate
diffractometer
1618 reflections with I > 2σ(I)
7824 measured reflectionsRint = 0.041
1989 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.101All H-atom parameters refined
S = 1.04Δρmax = 0.18 e Å3
1989 reflectionsΔρmin = 0.14 e Å3
167 parameters
Special details top

Experimental. Cooling Device: Oxford Cryosystems Cryostream 600. Imaging plate detector. Frames collected: 133. Seconds exposure per frame: 180. Degrees rotation per frame: 1.5. Crystal-detector distance (mm): 70.0

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
xyzUiso*/Ueq
O10.46460 (17)0.20119 (8)0.24316 (7)0.0417 (3)
N10.31364 (17)0.13055 (8)0.25724 (7)0.0274 (3)
N20.2107 (3)0.09139 (10)0.30952 (11)0.0471 (3)
H2A0.114 (3)0.1495 (15)0.3104 (12)0.0529 (11)*
H2B0.317 (3)0.0991 (14)0.2623 (13)0.0529 (11)*
C10.2392 (2)0.12590 (10)0.35662 (8)0.0282 (3)
C20.1046 (2)0.02590 (10)0.36838 (9)0.0311 (3)
H210.032 (3)0.0296 (13)0.4281 (12)0.0529 (11)*
H220.216 (3)0.0332 (14)0.3748 (12)0.0529 (11)*
C30.0812 (2)0.00122 (10)0.28541 (9)0.0300 (3)
H310.197 (3)0.0590 (14)0.2763 (12)0.0529 (11)*
C40.0425 (2)0.00881 (11)0.19495 (9)0.0329 (3)
H410.073 (3)0.0298 (13)0.1371 (12)0.0529 (11)*
H420.159 (3)0.0678 (14)0.2042 (12)0.0529 (11)*
C50.1728 (2)0.08874 (11)0.16905 (8)0.0308 (3)
C60.4609 (3)0.12765 (14)0.42811 (10)0.0406 (4)
H610.545 (3)0.1949 (14)0.4229 (12)0.0529 (11)*
H620.569 (3)0.0673 (14)0.4148 (12)0.0529 (11)*
H630.415 (3)0.1198 (13)0.4950 (13)0.0529 (11)*
C70.0874 (3)0.22064 (11)0.37282 (11)0.0396 (3)
H710.054 (3)0.2228 (13)0.4410 (13)0.0529 (11)*
H720.070 (3)0.2211 (13)0.3335 (12)0.0529 (11)*
H730.175 (3)0.2829 (14)0.3599 (12)0.0529 (11)*
C80.0025 (3)0.17256 (13)0.12663 (11)0.0439 (4)
H810.128 (3)0.1862 (13)0.1671 (12)0.0529 (11)*
H820.068 (3)0.1477 (13)0.0618 (13)0.0529 (11)*
H830.085 (3)0.2351 (15)0.1202 (12)0.0529 (11)*
C90.3451 (3)0.06182 (15)0.09690 (10)0.0466 (4)
H910.467 (3)0.0109 (14)0.1262 (12)0.0529 (11)*
H920.255 (3)0.0272 (13)0.0418 (12)0.0529 (11)*
H930.421 (3)0.1224 (14)0.0765 (12)0.0529 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0385 (5)0.0427 (6)0.0452 (6)0.0127 (4)0.0104 (4)0.0065 (4)
N10.0269 (5)0.0293 (5)0.0268 (5)0.0027 (4)0.0059 (4)0.0024 (4)
N20.0457 (8)0.0297 (7)0.0677 (9)0.0092 (6)0.0139 (6)0.0015 (6)
C10.0314 (6)0.0298 (6)0.0241 (6)0.0011 (5)0.0065 (4)0.0024 (5)
C20.0384 (7)0.0285 (7)0.0272 (6)0.0001 (6)0.0073 (5)0.0045 (5)
C30.0311 (6)0.0230 (6)0.0369 (7)0.0012 (5)0.0075 (5)0.0014 (5)
C40.0322 (7)0.0333 (7)0.0328 (7)0.0012 (6)0.0023 (5)0.0078 (5)
C50.0292 (6)0.0398 (7)0.0234 (6)0.0023 (5)0.0026 (5)0.0012 (5)
C60.0383 (8)0.0540 (9)0.0287 (7)0.0040 (7)0.0012 (5)0.0065 (6)
C70.0419 (8)0.0294 (7)0.0498 (8)0.0019 (6)0.0148 (7)0.0082 (6)
C80.0404 (8)0.0509 (9)0.0396 (8)0.0056 (7)0.0006 (6)0.0173 (7)
C90.0400 (8)0.0727 (12)0.0284 (7)0.0003 (8)0.0097 (6)0.0048 (7)
Geometric parameters (Å, º) top
O1—N11.2870 (13)C4—H421.009 (18)
N1—C51.4926 (16)C5—C91.5283 (19)
N1—C11.4982 (15)C5—C81.5295 (19)
N2—C31.4667 (17)C6—H611.000 (18)
N2—H2A0.933 (19)C6—H621.025 (18)
N2—H2B0.851 (19)C6—H631.003 (17)
C1—C61.5209 (19)C7—H710.993 (18)
C1—C21.5226 (17)C7—H721.001 (18)
C1—C71.5326 (18)C7—H730.977 (18)
C2—C31.5129 (19)C8—H811.004 (18)
C2—H210.974 (17)C8—H821.000 (18)
C2—H220.991 (18)C8—H830.947 (19)
C3—C41.5222 (18)C9—H911.011 (18)
C3—H310.995 (18)C9—H920.984 (17)
C4—C51.5285 (19)C9—H930.955 (18)
C4—H411.020 (17)
O1—N1—C5116.04 (10)N1—C5—C9107.31 (11)
O1—N1—C1115.91 (10)N1—C5—C4109.58 (10)
C5—N1—C1124.39 (9)C9—C5—C4109.71 (12)
C3—N2—H2A110.1 (11)N1—C5—C8108.79 (12)
C3—N2—H2B104.7 (12)C9—C5—C8109.67 (12)
H2A—N2—H2B106.7 (16)C4—C5—C8111.67 (11)
N1—C1—C6107.59 (10)C1—C6—H61109.7 (10)
N1—C1—C2109.57 (10)C1—C6—H62110.1 (9)
C6—C1—C2109.62 (11)H61—C6—H62110.1 (13)
N1—C1—C7109.32 (11)C1—C6—H63108.7 (10)
C6—C1—C7109.60 (11)H61—C6—H63109.5 (13)
C2—C1—C7111.07 (11)H62—C6—H63108.6 (13)
C3—C2—C1114.57 (10)C1—C7—H71109.9 (10)
C3—C2—H21109.5 (10)C1—C7—H72114.5 (10)
C1—C2—H21108.7 (10)H71—C7—H72105.2 (13)
C3—C2—H22107.1 (10)C1—C7—H73108.5 (10)
C1—C2—H22109.7 (10)H71—C7—H73108.4 (14)
H21—C2—H22107.0 (14)H72—C7—H73110.2 (14)
N2—C3—C2108.99 (11)C5—C8—H81112.9 (10)
N2—C3—C4114.60 (11)C5—C8—H82107.1 (10)
C2—C3—C4107.45 (11)H81—C8—H82108.5 (14)
N2—C3—H31107.2 (10)C5—C8—H83109.7 (11)
C2—C3—H31109.7 (10)H81—C8—H83108.6 (14)
C4—C3—H31108.8 (10)H82—C8—H83110.1 (14)
C3—C4—C5114.32 (10)C5—C9—H91110.4 (9)
C3—C4—H41110.9 (9)C5—C9—H92107.3 (10)
C5—C4—H41108.8 (9)H91—C9—H92107.3 (14)
C3—C4—H42108.7 (9)C5—C9—H93111.2 (11)
C5—C4—H42108.7 (10)H91—C9—H93109.6 (14)
H41—C4—H42105.0 (13)H92—C9—H93110.9 (14)
O1—N1—C1—C648.68 (14)N2—C3—C4—C5178.76 (12)
C5—N1—C1—C6153.81 (12)C2—C3—C4—C559.98 (14)
O1—N1—C1—C2167.80 (10)O1—N1—C5—C948.80 (15)
C5—N1—C1—C234.70 (15)C1—N1—C5—C9153.72 (12)
O1—N1—C1—C770.27 (13)O1—N1—C5—C4167.87 (10)
C5—N1—C1—C787.24 (14)C1—N1—C5—C434.65 (15)
N1—C1—C2—C346.50 (14)O1—N1—C5—C869.79 (13)
C6—C1—C2—C3164.36 (11)C1—N1—C5—C887.69 (14)
C7—C1—C2—C374.38 (14)C3—C4—C5—N146.21 (14)
C1—C2—C3—N2175.07 (11)C3—C4—C5—C9163.78 (11)
C1—C2—C3—C460.21 (14)C3—C4—C5—C874.41 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.933 (19)2.27 (2)3.153 (2)158 (3)
Symmetry code: (i) x+1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC9H19N2O
Mr171.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)160
a, b, c (Å)5.721 (2), 12.919 (3), 13.955 (4)
β (°) 96.61 (4)
V3)1024.6 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.31 × 0.24 × 0.20
Data collection
DiffractometerStoe IPDS imaging plate
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
7824, 1989, 1618
Rint0.041
(sin θ/λ)max1)0.619
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.101, 1.04
No. of reflections1989
No. of parameters167
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.18, 0.14

Computer programs: IPDS (Stoe & Cie, 1996), IPDS, X-RED (Stoe & Cie, 1996), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), CAMERON (Pearce & Watkin, 1993) and ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.933 (19)2.27 (2)3.153 (2)158 (3)
Symmetry code: (i) x+1/2, y1/2, z+1/2.
 

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