Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032898/cf2110sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032898/cf2110Isup2.hkl |
CCDC reference: 657697
Key indicators
- Single-crystal X-ray study
- T = 160 K
- Mean (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
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.
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.
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).
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).
C9H19N2O | F(000) = 380 |
Mr = 171.26 | Dx = 1.110 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 943 reflections |
a = 5.721 (2) Å | θ = 3.1–26.1° |
b = 12.919 (3) Å | µ = 0.07 mm−1 |
c = 13.955 (4) Å | T = 160 K |
β = 96.61 (4)° | Block, orange |
V = 1024.6 (5) Å3 | 0.31 × 0.24 × 0.20 mm |
Z = 4 |
Stoe IPDS imaging plate diffractometer | 1618 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 26.1°, θmin = 1.7° |
φ scans with 1.5° steps | h = −7→7 |
7824 measured reflections | k = −15→15 |
1989 independent reflections | l = −16→17 |
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)] = 0.040 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.101 | All 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 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
C9H19N2O | V = 1024.6 (5) Å3 |
Mr = 171.26 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 5.721 (2) Å | µ = 0.07 mm−1 |
b = 12.919 (3) Å | T = 160 K |
c = 13.955 (4) Å | 0.31 × 0.24 × 0.20 mm |
β = 96.61 (4)° |
Stoe IPDS imaging plate diffractometer | 1618 reflections with I > 2σ(I) |
7824 measured reflections | Rint = 0.041 |
1989 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.101 | All H-atom parameters refined |
S = 1.04 | Δρmax = 0.18 e Å−3 |
1989 reflections | Δρmin = −0.14 e Å−3 |
167 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.46460 (17) | 0.20119 (8) | 0.24316 (7) | 0.0417 (3) | |
N1 | 0.31364 (17) | 0.13055 (8) | 0.25724 (7) | 0.0274 (3) | |
N2 | −0.2107 (3) | −0.09139 (10) | 0.30952 (11) | 0.0471 (3) | |
H2A | −0.114 (3) | −0.1495 (15) | 0.3104 (12) | 0.0529 (11)* | |
H2B | −0.317 (3) | −0.0991 (14) | 0.2623 (13) | 0.0529 (11)* | |
C1 | 0.2392 (2) | 0.12590 (10) | 0.35662 (8) | 0.0282 (3) | |
C2 | 0.1046 (2) | 0.02590 (10) | 0.36838 (9) | 0.0311 (3) | |
H21 | 0.032 (3) | 0.0296 (13) | 0.4281 (12) | 0.0529 (11)* | |
H22 | 0.216 (3) | −0.0332 (14) | 0.3748 (12) | 0.0529 (11)* | |
C3 | −0.0812 (2) | 0.00122 (10) | 0.28541 (9) | 0.0300 (3) | |
H31 | −0.197 (3) | 0.0590 (14) | 0.2763 (12) | 0.0529 (11)* | |
C4 | 0.0425 (2) | −0.00881 (11) | 0.19495 (9) | 0.0329 (3) | |
H41 | −0.073 (3) | −0.0298 (13) | 0.1371 (12) | 0.0529 (11)* | |
H42 | 0.159 (3) | −0.0678 (14) | 0.2042 (12) | 0.0529 (11)* | |
C5 | 0.1728 (2) | 0.08874 (11) | 0.16905 (8) | 0.0308 (3) | |
C6 | 0.4609 (3) | 0.12765 (14) | 0.42811 (10) | 0.0406 (4) | |
H61 | 0.545 (3) | 0.1949 (14) | 0.4229 (12) | 0.0529 (11)* | |
H62 | 0.569 (3) | 0.0673 (14) | 0.4148 (12) | 0.0529 (11)* | |
H63 | 0.415 (3) | 0.1198 (13) | 0.4950 (13) | 0.0529 (11)* | |
C7 | 0.0874 (3) | 0.22064 (11) | 0.37282 (11) | 0.0396 (3) | |
H71 | 0.054 (3) | 0.2228 (13) | 0.4410 (13) | 0.0529 (11)* | |
H72 | −0.070 (3) | 0.2211 (13) | 0.3335 (12) | 0.0529 (11)* | |
H73 | 0.175 (3) | 0.2829 (14) | 0.3599 (12) | 0.0529 (11)* | |
C8 | 0.0025 (3) | 0.17256 (13) | 0.12663 (11) | 0.0439 (4) | |
H81 | −0.128 (3) | 0.1862 (13) | 0.1671 (12) | 0.0529 (11)* | |
H82 | −0.068 (3) | 0.1477 (13) | 0.0618 (13) | 0.0529 (11)* | |
H83 | 0.085 (3) | 0.2351 (15) | 0.1202 (12) | 0.0529 (11)* | |
C9 | 0.3451 (3) | 0.06182 (15) | 0.09690 (10) | 0.0466 (4) | |
H91 | 0.467 (3) | 0.0109 (14) | 0.1262 (12) | 0.0529 (11)* | |
H92 | 0.255 (3) | 0.0272 (13) | 0.0418 (12) | 0.0529 (11)* | |
H93 | 0.421 (3) | 0.1224 (14) | 0.0765 (12) | 0.0529 (11)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0385 (5) | 0.0427 (6) | 0.0452 (6) | −0.0127 (4) | 0.0104 (4) | 0.0065 (4) |
N1 | 0.0269 (5) | 0.0293 (5) | 0.0268 (5) | −0.0027 (4) | 0.0059 (4) | 0.0024 (4) |
N2 | 0.0457 (8) | 0.0297 (7) | 0.0677 (9) | −0.0092 (6) | 0.0139 (6) | −0.0015 (6) |
C1 | 0.0314 (6) | 0.0298 (6) | 0.0241 (6) | −0.0011 (5) | 0.0065 (4) | −0.0024 (5) |
C2 | 0.0384 (7) | 0.0285 (7) | 0.0272 (6) | 0.0001 (6) | 0.0073 (5) | 0.0045 (5) |
C3 | 0.0311 (6) | 0.0230 (6) | 0.0369 (7) | −0.0012 (5) | 0.0075 (5) | −0.0014 (5) |
C4 | 0.0322 (7) | 0.0333 (7) | 0.0328 (7) | 0.0012 (6) | 0.0023 (5) | −0.0078 (5) |
C5 | 0.0292 (6) | 0.0398 (7) | 0.0234 (6) | 0.0023 (5) | 0.0026 (5) | 0.0012 (5) |
C6 | 0.0383 (8) | 0.0540 (9) | 0.0287 (7) | −0.0040 (7) | 0.0012 (5) | −0.0065 (6) |
C7 | 0.0419 (8) | 0.0294 (7) | 0.0498 (8) | −0.0019 (6) | 0.0148 (7) | −0.0082 (6) |
C8 | 0.0404 (8) | 0.0509 (9) | 0.0396 (8) | 0.0056 (7) | 0.0006 (6) | 0.0173 (7) |
C9 | 0.0400 (8) | 0.0727 (12) | 0.0284 (7) | 0.0003 (8) | 0.0097 (6) | −0.0048 (7) |
O1—N1 | 1.2870 (13) | C4—H42 | 1.009 (18) |
N1—C5 | 1.4926 (16) | C5—C9 | 1.5283 (19) |
N1—C1 | 1.4982 (15) | C5—C8 | 1.5295 (19) |
N2—C3 | 1.4667 (17) | C6—H61 | 1.000 (18) |
N2—H2A | 0.933 (19) | C6—H62 | 1.025 (18) |
N2—H2B | 0.851 (19) | C6—H63 | 1.003 (17) |
C1—C6 | 1.5209 (19) | C7—H71 | 0.993 (18) |
C1—C2 | 1.5226 (17) | C7—H72 | 1.001 (18) |
C1—C7 | 1.5326 (18) | C7—H73 | 0.977 (18) |
C2—C3 | 1.5129 (19) | C8—H81 | 1.004 (18) |
C2—H21 | 0.974 (17) | C8—H82 | 1.000 (18) |
C2—H22 | 0.991 (18) | C8—H83 | 0.947 (19) |
C3—C4 | 1.5222 (18) | C9—H91 | 1.011 (18) |
C3—H31 | 0.995 (18) | C9—H92 | 0.984 (17) |
C4—C5 | 1.5285 (19) | C9—H93 | 0.955 (18) |
C4—H41 | 1.020 (17) | ||
O1—N1—C5 | 116.04 (10) | N1—C5—C9 | 107.31 (11) |
O1—N1—C1 | 115.91 (10) | N1—C5—C4 | 109.58 (10) |
C5—N1—C1 | 124.39 (9) | C9—C5—C4 | 109.71 (12) |
C3—N2—H2A | 110.1 (11) | N1—C5—C8 | 108.79 (12) |
C3—N2—H2B | 104.7 (12) | C9—C5—C8 | 109.67 (12) |
H2A—N2—H2B | 106.7 (16) | C4—C5—C8 | 111.67 (11) |
N1—C1—C6 | 107.59 (10) | C1—C6—H61 | 109.7 (10) |
N1—C1—C2 | 109.57 (10) | C1—C6—H62 | 110.1 (9) |
C6—C1—C2 | 109.62 (11) | H61—C6—H62 | 110.1 (13) |
N1—C1—C7 | 109.32 (11) | C1—C6—H63 | 108.7 (10) |
C6—C1—C7 | 109.60 (11) | H61—C6—H63 | 109.5 (13) |
C2—C1—C7 | 111.07 (11) | H62—C6—H63 | 108.6 (13) |
C3—C2—C1 | 114.57 (10) | C1—C7—H71 | 109.9 (10) |
C3—C2—H21 | 109.5 (10) | C1—C7—H72 | 114.5 (10) |
C1—C2—H21 | 108.7 (10) | H71—C7—H72 | 105.2 (13) |
C3—C2—H22 | 107.1 (10) | C1—C7—H73 | 108.5 (10) |
C1—C2—H22 | 109.7 (10) | H71—C7—H73 | 108.4 (14) |
H21—C2—H22 | 107.0 (14) | H72—C7—H73 | 110.2 (14) |
N2—C3—C2 | 108.99 (11) | C5—C8—H81 | 112.9 (10) |
N2—C3—C4 | 114.60 (11) | C5—C8—H82 | 107.1 (10) |
C2—C3—C4 | 107.45 (11) | H81—C8—H82 | 108.5 (14) |
N2—C3—H31 | 107.2 (10) | C5—C8—H83 | 109.7 (11) |
C2—C3—H31 | 109.7 (10) | H81—C8—H83 | 108.6 (14) |
C4—C3—H31 | 108.8 (10) | H82—C8—H83 | 110.1 (14) |
C3—C4—C5 | 114.32 (10) | C5—C9—H91 | 110.4 (9) |
C3—C4—H41 | 110.9 (9) | C5—C9—H92 | 107.3 (10) |
C5—C4—H41 | 108.8 (9) | H91—C9—H92 | 107.3 (14) |
C3—C4—H42 | 108.7 (9) | C5—C9—H93 | 111.2 (11) |
C5—C4—H42 | 108.7 (10) | H91—C9—H93 | 109.6 (14) |
H41—C4—H42 | 105.0 (13) | H92—C9—H93 | 110.9 (14) |
O1—N1—C1—C6 | −48.68 (14) | N2—C3—C4—C5 | 178.76 (12) |
C5—N1—C1—C6 | 153.81 (12) | C2—C3—C4—C5 | −59.98 (14) |
O1—N1—C1—C2 | −167.80 (10) | O1—N1—C5—C9 | 48.80 (15) |
C5—N1—C1—C2 | 34.70 (15) | C1—N1—C5—C9 | −153.72 (12) |
O1—N1—C1—C7 | 70.27 (13) | O1—N1—C5—C4 | 167.87 (10) |
C5—N1—C1—C7 | −87.24 (14) | C1—N1—C5—C4 | −34.65 (15) |
N1—C1—C2—C3 | −46.50 (14) | O1—N1—C5—C8 | −69.79 (13) |
C6—C1—C2—C3 | −164.36 (11) | C1—N1—C5—C8 | 87.69 (14) |
C7—C1—C2—C3 | 74.38 (14) | C3—C4—C5—N1 | 46.21 (14) |
C1—C2—C3—N2 | −175.07 (11) | C3—C4—C5—C9 | 163.78 (11) |
C1—C2—C3—C4 | 60.21 (14) | C3—C4—C5—C8 | −74.41 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.933 (19) | 2.27 (2) | 3.153 (2) | 158 (3) |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H19N2O |
Mr | 171.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 160 |
a, b, c (Å) | 5.721 (2), 12.919 (3), 13.955 (4) |
β (°) | 96.61 (4) |
V (Å3) | 1024.6 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.31 × 0.24 × 0.20 |
Data collection | |
Diffractometer | Stoe IPDS imaging plate |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7824, 1989, 1618 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.101, 1.04 |
No. of reflections | 1989 |
No. of parameters | 167 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 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).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.933 (19) | 2.27 (2) | 3.153 (2) | 158 (3) |
Symmetry code: (i) −x+1/2, y−1/2, −z+1/2. |
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).