PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1197.
Published online 2008 June 7. doi:  10.1107/S1600536808016085
PMCID: PMC2961723

4,4,5,5-Tetra­methyl-2-(4-pyridyl)­imidazolidin-1-oxyl-3-oxide trichloroacetic acid solvate

Abstract

In the title compound, C12H16N3O2·C2HCl3O2, the imidazolidine ring adopts a twist conformation. The crystal structure is stabilized by inter­molecular O—H(...)N hydrogen bonds.

Related literature

For related literature, see: Zhang et al. (2006 [triangle]); Ullman et al. (1972 [triangle]); Oshio et al. (2002 [triangle]); Vostrikova et al. (2000 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1197-scheme1.jpg

Experimental

Crystal data

  • C12H16N3O2·C2HCl3O2
  • M r = 397.66
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1197-efi1.jpg
  • a = 10.003 (2) Å
  • b = 21.036 (4) Å
  • c = 9.2796 (19) Å
  • β = 115.33 (3)°
  • V = 1764.9 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.54 mm−1
  • T = 293 (2) K
  • 0.20 × 0.20 × 0.20 mm

Data collection

  • Bruker SMART 1K CCD area-detector diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.895, T max = 0.898
  • 14888 measured reflections
  • 3100 independent reflections
  • 2041 reflections with I > 2σ(I)
  • R int = 0.098

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.132
  • S = 1.06
  • 3100 reflections
  • 217 parameters
  • H-atom parameters constrained
  • Δρmax = 0.36 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808016085/rz2217sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016085/rz2217Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Transition metal compounds containing nitroxide radical ligands are of great interest, as these compounds play an important role in molecule-based magnetic materials (Oshio et al., 2002; Vostrikova et al., 2000). In order to investigate the crystal structure of such ligands, the title compound has been synthesized and its crystal structure is reported here.

In the title compound (Fig. 1), the imidazole ring adopts a twist conformation, with atoms C7 and C10 displaced by 0.218 (4) and 0.240 (4) Å respectively on opposite sides of the plane through atoms N2, N3, C6. The dihedral angle between the pyridine and the mean plane of the imidazole ring is 20.31 (27)°. This angle is smaller than that of 25.66 (15)° observed in the unsolvated compound (Zhang et al., 2006). In the crystal structure, an intermolecular hydrogen bonding interaction involving the hydroxyl group of the trichloroacetic acid and the N atom of the pyridine ring is observed (Table 1).

Experimental

4,4,5,5-Tetramethyl-2-(4-pyridyl)imidazolin-1-oxyl-3-oxide was prepared according to the published method (Ullman et al., 1972). All chemicals used (reagent grade) were commercially available. 2-(4-Pyridyl)-4,4,5,5-teramethylimidazolin-1-oxyl-3-oxide (0.024 g, 0.1 mmol) was dissolved in ethanol (10 ml). Trichloroacetic acid (0.016 g, 0.1 mmol) was added slowly with stirring. The resulted solution was continuously stirred for about 30 min at room temperature and then filtered. The filtrate was slowly evaporated at room temperature over several days, to give colourless crystals suitable for X-ray analysis.

Refinement

All H atoms were placed at calculated positions and allowed to ride on their parent atoms, with C—H = 0.93–0.96 Å, O—H = 0.82 Å, and with Uiso(H) = 1.5 Ueq(C, O) or 1.2 Ueq(C) for aromatic H atoms.

Figures

Fig. 1.
The molecular structure of the title compound with the atom-numbering scheme. All hydrogen atoms are omitted except for H4B. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
Packing diagram of the title compound viewed along the b axis. Hydrogen bonds are shown as dashed lines. All hydrogen atoms are omitted except for H4B.

Crystal data

C12H16N3O2·C2HCl3O2F000 = 820
Mr = 397.66Dx = 1.497 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 12720 reflections
a = 10.003 (2) Åθ = 1.0–27.6º
b = 21.036 (4) ŵ = 0.54 mm1
c = 9.2796 (19) ÅT = 293 (2) K
β = 115.33 (3)ºPrism, colourless
V = 1764.9 (7) Å30.20 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker SMART 1K CCD area-detector diffractometer3100 independent reflections
Radiation source: fine-focus sealed tube2041 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.098
Detector resolution: 8.192 pixels mm-1θmax = 25.0º
T = 293(2) Kθmin = 2.5º
thin–slice ω scansh = −11→11
Absorption correction: multi-scan(CrystalClear; Rigaku, 2005)k = −25→25
Tmin = 0.895, Tmax = 0.898l = −11→11
14888 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.132  w = 1/[σ2(Fo2) + (0.0424P)2 + 1.1663P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
3100 reflectionsΔρmax = 0.36 e Å3
217 parametersΔρmin = −0.26 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
Cl10.23783 (13)0.11481 (6)0.16145 (14)0.0544 (4)
Cl20.44021 (13)0.19710 (5)0.40583 (14)0.0544 (4)
Cl30.50692 (15)0.06513 (6)0.41125 (15)0.0620 (4)
N31.0715 (4)−0.17317 (15)0.4059 (4)0.0378 (8)
O10.9245 (3)−0.03239 (13)0.2203 (3)0.0485 (8)
N20.9604 (3)−0.08379 (15)0.2999 (4)0.0330 (8)
N11.3320 (4)−0.10702 (18)0.0574 (4)0.0431 (9)
C140.5057 (4)0.1426 (2)0.1725 (5)0.0396 (10)
C61.0677 (4)−0.12466 (18)0.3092 (4)0.0326 (9)
O40.5301 (4)0.09179 (15)0.1183 (4)0.0594 (9)
H4B0.57060.09950.05980.089*
C31.1616 (4)−0.11841 (18)0.2243 (4)0.0318 (9)
O21.1539 (4)−0.22208 (15)0.4388 (4)0.0679 (10)
O30.5285 (4)0.19655 (16)0.1466 (4)0.0700 (10)
C70.8677 (4)−0.11090 (19)0.3775 (5)0.0365 (10)
C100.9750 (4)−0.15972 (19)0.4916 (5)0.0363 (10)
C51.3255 (5)−0.1617 (2)0.1249 (5)0.0456 (11)
H5A1.3779−0.19630.11340.055*
C130.4289 (4)0.13093 (18)0.2862 (5)0.0369 (10)
C41.2440 (4)−0.16910 (19)0.2113 (5)0.0396 (10)
H4A1.2443−0.20770.26040.048*
C21.1702 (5)−0.0613 (2)0.1541 (5)0.0513 (12)
H2A1.1178−0.02600.16220.062*
C120.9050 (5)−0.2207 (2)0.5118 (6)0.0630 (14)
H12A0.8399−0.23700.40900.094*
H12B0.8498−0.21250.57270.094*
H12C0.9809−0.25140.56670.094*
C90.7334 (5)−0.1403 (2)0.2419 (5)0.0587 (13)
H9A0.7651−0.17390.19360.088*
H9B0.6828−0.10840.16360.088*
H9C0.6677−0.15730.28320.088*
C111.0795 (5)−0.1329 (2)0.6540 (5)0.0599 (13)
H11A1.1223−0.09400.63930.090*
H11B1.1566−0.16310.70880.090*
H11C1.0252−0.12470.71600.090*
C11.2570 (5)−0.0571 (2)0.0721 (5)0.0537 (13)
H1B1.2633−0.01860.02620.064*
C80.8203 (5)−0.0578 (2)0.4560 (6)0.0582 (13)
H8A0.9059−0.03990.54130.087*
H8B0.7546−0.07440.49760.087*
H8C0.7705−0.02540.37860.087*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0439 (7)0.0609 (8)0.0638 (8)−0.0087 (6)0.0282 (6)−0.0041 (6)
Cl20.0639 (8)0.0492 (7)0.0615 (8)−0.0039 (6)0.0378 (6)−0.0122 (6)
Cl30.0845 (9)0.0510 (7)0.0616 (8)0.0196 (7)0.0417 (7)0.0269 (6)
N30.043 (2)0.0336 (19)0.043 (2)0.0057 (17)0.0234 (17)0.0060 (16)
O10.0541 (19)0.0439 (18)0.059 (2)0.0196 (15)0.0354 (16)0.0186 (15)
N20.0348 (19)0.0324 (19)0.034 (2)0.0051 (16)0.0171 (16)0.0023 (15)
N10.042 (2)0.053 (2)0.041 (2)0.0010 (19)0.0237 (18)−0.0032 (18)
C140.032 (2)0.052 (3)0.037 (3)0.001 (2)0.016 (2)0.007 (2)
C60.034 (2)0.034 (2)0.031 (2)0.004 (2)0.0153 (19)0.0018 (18)
O40.071 (2)0.069 (2)0.061 (2)0.0061 (19)0.0502 (19)−0.0005 (17)
C30.031 (2)0.036 (2)0.028 (2)0.0002 (19)0.0128 (18)−0.0016 (17)
O20.082 (2)0.053 (2)0.093 (3)0.0336 (19)0.061 (2)0.0324 (18)
O30.100 (3)0.055 (2)0.077 (3)−0.011 (2)0.058 (2)0.0171 (18)
C70.030 (2)0.044 (3)0.042 (3)0.001 (2)0.022 (2)0.000 (2)
C100.036 (2)0.043 (3)0.035 (2)−0.001 (2)0.021 (2)0.0006 (19)
C50.037 (2)0.046 (3)0.061 (3)0.003 (2)0.027 (2)−0.012 (2)
C130.041 (2)0.033 (2)0.043 (3)0.0003 (19)0.024 (2)0.0059 (19)
C40.043 (3)0.030 (2)0.052 (3)0.000 (2)0.026 (2)−0.0032 (19)
C20.060 (3)0.049 (3)0.062 (3)0.019 (2)0.043 (3)0.016 (2)
C120.061 (3)0.057 (3)0.084 (4)0.000 (3)0.044 (3)0.019 (3)
C90.036 (3)0.079 (4)0.051 (3)−0.012 (3)0.010 (2)0.005 (3)
C110.055 (3)0.075 (4)0.045 (3)0.007 (3)0.017 (2)0.002 (2)
C10.065 (3)0.055 (3)0.058 (3)0.017 (3)0.041 (3)0.023 (2)
C80.064 (3)0.065 (3)0.064 (3)0.012 (3)0.045 (3)0.007 (3)

Geometric parameters (Å, °)

Cl1—C131.793 (4)C10—C121.512 (6)
Cl2—C131.754 (4)C10—C111.528 (6)
Cl3—C131.760 (4)C5—C41.375 (5)
N3—O21.271 (4)C5—H5A0.9300
N3—C61.349 (5)C4—H4A0.9300
N3—C101.517 (5)C2—C11.381 (5)
O1—N21.272 (4)C2—H2A0.9300
N2—C61.349 (5)C12—H12A0.9600
N2—C71.508 (5)C12—H12B0.9600
N1—C51.324 (5)C12—H12C0.9600
N1—C11.331 (5)C9—H9A0.9600
C14—O31.202 (5)C9—H9B0.9600
C14—O41.249 (5)C9—H9C0.9600
C14—C131.568 (5)C11—H11A0.9600
C6—C31.467 (5)C11—H11B0.9600
O4—H4B0.8200C11—H11C0.9600
C3—C41.385 (5)C1—H1B0.9300
C3—C21.387 (5)C8—H8A0.9600
C7—C81.516 (5)C8—H8B0.9600
C7—C91.525 (6)C8—H8C0.9600
C7—C101.535 (6)
O2—N3—C6127.0 (3)Cl2—C13—Cl1108.7 (2)
O2—N3—C10121.2 (3)Cl3—C13—Cl1109.1 (2)
C6—N3—C10111.4 (3)C5—C4—C3119.1 (4)
O1—N2—C6126.8 (3)C5—C4—H4A120.4
O1—N2—C7121.3 (3)C3—C4—H4A120.4
C6—N2—C7111.3 (3)C1—C2—C3119.6 (4)
C5—N1—C1119.5 (3)C1—C2—H2A120.2
O3—C14—O4129.9 (4)C3—C2—H2A120.2
O3—C14—C13118.1 (4)C10—C12—H12A109.5
O4—C14—C13111.9 (4)C10—C12—H12B109.5
N3—C6—N2108.6 (3)H12A—C12—H12B109.5
N3—C6—C3125.7 (3)C10—C12—H12C109.5
N2—C6—C3125.7 (3)H12A—C12—H12C109.5
C14—O4—H4B109.5H12B—C12—H12C109.5
C4—C3—C2117.9 (4)C7—C9—H9A109.5
C4—C3—C6121.3 (3)C7—C9—H9B109.5
C2—C3—C6120.8 (3)H9A—C9—H9B109.5
N2—C7—C8109.4 (3)C7—C9—H9C109.5
N2—C7—C9105.3 (3)H9A—C9—H9C109.5
C8—C7—C9110.4 (4)H9B—C9—H9C109.5
N2—C7—C10101.0 (3)C10—C11—H11A109.5
C8—C7—C10115.6 (3)C10—C11—H11B109.5
C9—C7—C10114.0 (3)H11A—C11—H11B109.5
C12—C10—N3109.8 (3)C10—C11—H11C109.5
C12—C10—C11110.4 (4)H11A—C11—H11C109.5
N3—C10—C11105.4 (3)H11B—C11—H11C109.5
C12—C10—C7115.4 (3)N1—C1—C2121.4 (4)
N3—C10—C7100.2 (3)N1—C1—H1B119.3
C11—C10—C7114.5 (3)C2—C1—H1B119.3
N1—C5—C4122.4 (4)C7—C8—H8A109.5
N1—C5—H5A118.8C7—C8—H8B109.5
C4—C5—H5A118.8H8A—C8—H8B109.5
C14—C13—Cl2112.6 (3)C7—C8—H8C109.5
C14—C13—Cl3111.1 (3)H8A—C8—H8C109.5
Cl2—C13—Cl3108.5 (2)H8B—C8—H8C109.5
C14—C13—Cl1106.8 (3)
O2—N3—C6—N2177.0 (4)N2—C7—C10—C12−143.3 (3)
C10—N3—C6—N2−9.8 (4)C8—C7—C10—C1298.8 (4)
O2—N3—C6—C3−1.2 (7)C9—C7—C10—C12−30.8 (5)
C10—N3—C6—C3172.0 (3)N2—C7—C10—N3−25.4 (3)
O1—N2—C6—N3179.8 (3)C8—C7—C10—N3−143.4 (3)
C7—N2—C6—N3−9.0 (4)C9—C7—C10—N387.0 (4)
O1—N2—C6—C3−2.0 (6)N2—C7—C10—C1186.8 (4)
C7—N2—C6—C3169.3 (4)C8—C7—C10—C11−31.1 (5)
N3—C6—C3—C413.2 (6)C9—C7—C10—C11−160.7 (4)
N2—C6—C3—C4−164.8 (4)C1—N1—C5—C4−0.3 (6)
N3—C6—C3—C2−166.9 (4)O3—C14—C13—Cl2−18.8 (5)
N2—C6—C3—C215.1 (6)O4—C14—C13—Cl2163.2 (3)
O1—N2—C7—C8−43.0 (5)O3—C14—C13—Cl3−140.6 (4)
C6—N2—C7—C8145.2 (3)O4—C14—C13—Cl341.3 (4)
O1—N2—C7—C975.8 (4)O3—C14—C13—Cl1100.5 (4)
C6—N2—C7—C9−96.0 (4)O4—C14—C13—Cl1−77.5 (4)
O1—N2—C7—C10−165.3 (3)N1—C5—C4—C32.2 (6)
C6—N2—C7—C1022.9 (4)C2—C3—C4—C5−2.6 (6)
O2—N3—C10—C12−41.2 (5)C6—C3—C4—C5177.3 (4)
C6—N3—C10—C12145.1 (4)C4—C3—C2—C11.2 (6)
O2—N3—C10—C1177.7 (4)C6—C3—C2—C1−178.7 (4)
C6—N3—C10—C11−95.9 (4)C5—N1—C1—C2−1.1 (7)
O2—N3—C10—C7−163.1 (4)C3—C2—C1—N10.7 (7)
C6—N3—C10—C723.2 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O4—H4B···N1i0.821.752.567 (7)173

Symmetry codes: (i) −x+2, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2217).

References

  • Oshio, H., Yamamoto, M. & Ito, T. (2002). Inorg. Chem.41, 5817–5820. [PubMed]
  • Rigaku. (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Ullman, E. F., Osiecki, J. H., Boocock, D. G. B. & Darcy, R. (1972). J. Am. Chem. Soc. , 94, 7049–7059.
  • Vostrikova, K. E., Luneau, D., Wernsdorfer, W., Rey, P. & Verdaguer, M. (2000). J. Am. Chem. Soc.122, 718–719.
  • Zhang, C.-X., Sun, D.-L. & Wang, X.-C. (2006). Acta Cryst. E62, o5666–o5667.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography