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Acta Cryst. (2012). E68, o218    [ doi:10.1107/S1600536811053979 ]

2-[3-Hydroxy-4-(2-hydroxyethoxy)phenyl]-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl 3-oxide

H.-P. Ma, L.-L. Jing, L. He, P.-C. Fan and Z.-P. Jia

Abstract top

In the title compound, C15H21N2O5, the imidazoline ring displays a twisted conformation. The mean plane of the imidazoline ring makes a dihedral angle of 22.55 (5)° with the benzene ring. In the crystal, O-H...O and C-H...O hydrogen bonds link the molecules into a layer parallel to the bc plane.

Comment top

Nitronyl nitroxides, which can react with free radicals such as OH, H2O2, and O2 (Blasig et al., 2002) to protect cells from the attack of free radicals have lots of biological properities as anticancer, antiradiation and antioxidation (Qin et al., 2009; Tanaka et al., 2007; Soule et al., 2007).

The molecular structure of the title compound is shown in Fig. 1. The nitronyl nitroxide ring and the phenyl rings are twisted with respect to each other making a dihedral angle of 22.55 (5)°. The puckering parameters of the nitronyl nitroxide ring are Q(2) = 0.2645 (17) Å and φ = 121.9 (4)° (Cremer & Pople, 1975). The pseudorotation parameters (Rao et al., 1981) for the nitronyl nitroxide ring are P = 283.2 (2)° and τ(M) = 27.1 (1)° for the C7—N1 reference bond with the closest puckering descriptor being twisted on C8—C9. The crystal structure is stabilized by O—H···O and C—H···O hydrogen bonds (Table 1).

Related literature top

For the biological activity of nitronyl nitroxides, see: Soule et al. (2007); Blasig et al. (2002); Qin et al. (2009); Tanaka et al. (2007). For puckering parameters, see: Cremer & Pople (1975). For pseudorotation parameters, see: Rao et al. (1981). For related structures, see: Jing, Ma, Fan et al. (2011); Jing, Ma, He et al. (2011).

Experimental top

To a solution of 3-hydroxy-4-(2-hydroxyethoxy)benzaldehyde (0.91 g, 5 mmol) in methanol (20 ml), 2,3-dimethyl-2,3-bis(hydroxylamino) butane (0.74 g, 5.0 mmol) was added. The mixture was stirring for 24 h at room temperature then filtered. The resulting white powder was suspended in the solution of dichloromethane (20.0 ml). An aqueous solution of NaIO4 (20 ml) was added to the reaction mixture and stirred for 15 min in an ice bath. The aqueous phase was extracted with CH2Cl2 and the combined organic layers were washed with brine (20 ml) and dried over Na2SO4. the solvent was removed to obtain a dark blue residue which was purified by flash column chromatography with the elution of dichloromethane/ methanol (10:1) to yield 0.70 g (45%) of the title compound as a dark blue powder. Single crystals of the title compound suitable for X-ray diffraction was recrystallized from hexane/dichloromethane (1:2).

Refinement top

H atoms were positioned geometrically and refined using a riding model, with C—Hmethyl = 0.96 Å, C—Hmethylene = 0.97 Å, C—Haryl = 0.93 Å and O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius.
2-[3-Hydroxy-4-(2-hydroxyethoxy)phenyl]-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl 3-oxide top
Crystal data top
C15H21N2O5F(000) = 660
Mr = 309.34Dx = 1.358 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2979 reflections
a = 9.787 (4) Åθ = 2.5–27.7°
b = 9.302 (3) ŵ = 0.10 mm−1
c = 16.657 (6) ÅT = 296 K
β = 93.525 (3)°Block, blue
V = 1513.5 (10) Å30.25 × 0.23 × 0.21 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer		2784 independent reflections
Radiation source: fine-focus sealed tube2172 reflections with I > 2σ(I)
graphiteRint = 0.023
φ and ω scansθmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)		h = −11→8
Tmin = 0.975, Tmax = 0.979k = −11→10
7023 measured reflectionsl = −20→19
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.103 w = 1/[σ2(Fo2) + (0.0486P)2 + 0.519P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2784 reflectionsΔρmax = 0.21 e Å−3
206 parametersΔρmin = −0.14 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0167 (18)
Crystal data top
C15H21N2O5V = 1513.5 (10) Å3
Mr = 309.34Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.787 (4) ŵ = 0.10 mm−1
b = 9.302 (3) ÅT = 296 K
c = 16.657 (6) Å0.25 × 0.23 × 0.21 mm
β = 93.525 (3)°
Data collection top
Bruker APEXII CCD
diffractometer		2784 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)		2172 reflections with I > 2σ(I)
Tmin = 0.975, Tmax = 0.979Rint = 0.023
7023 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.103Δρmax = 0.21 e Å−3
S = 1.01Δρmin = −0.14 e Å−3
2784 reflectionsAbsolute structure: ?
206 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
C10.84569 (17)0.65658 (17)0.96445 (9)0.0307 (4)
C20.90504 (16)0.61269 (17)0.89405 (9)0.0291 (4)
C30.86536 (16)0.48613 (17)0.85697 (9)0.0294 (4)
H30.90520.45770.81030.035*
C40.76514 (16)0.39970 (17)0.88925 (9)0.0287 (4)
C50.70732 (19)0.44374 (19)0.95909 (10)0.0399 (4)
H50.64090.38700.98120.048*
C60.74747 (19)0.57120 (19)0.99621 (10)0.0403 (5)
H60.70780.59951.04300.048*
C70.71796 (16)0.26786 (17)0.84938 (9)0.0276 (4)
C80.69965 (17)0.06957 (17)0.76020 (10)0.0330 (4)
C90.58253 (17)0.06193 (17)0.81818 (10)0.0330 (4)
C100.7809 (2)−0.0678 (2)0.75295 (14)0.0548 (6)
H10A0.8528−0.05260.71720.082*
H10B0.7214−0.14280.73200.082*
H10C0.8199−0.09520.80500.082*
C110.6547 (2)0.1276 (2)0.67686 (11)0.0498 (5)
H11A0.60490.21560.68240.075*
H11B0.59720.05820.64870.075*
H11C0.73400.14560.64710.075*
C120.6080 (2)−0.0420 (2)0.88796 (12)0.0538 (5)
H12A0.6964−0.02350.91410.081*
H12B0.6050−0.13890.86810.081*
H12C0.5387−0.02940.92570.081*
C130.44130 (18)0.0385 (2)0.77753 (12)0.0476 (5)
H13A0.37530.03080.81760.071*
H13B0.4411−0.04840.74640.071*
H13C0.41810.11830.74280.071*
C140.8384 (2)0.83103 (19)1.06967 (10)0.0397 (4)
H14A0.86550.76401.11230.048*
H14B0.73920.83471.06440.048*
C150.8949 (2)0.9769 (2)1.08947 (11)0.0419 (5)
H15A0.88170.99931.14530.050*
H15B0.99240.97841.08190.050*
N10.78767 (13)0.18428 (14)0.80059 (8)0.0290 (3)
N20.59145 (14)0.20965 (14)0.85370 (8)0.0328 (3)
O10.91259 (12)0.20380 (13)0.78261 (7)0.0408 (3)
O20.49072 (13)0.26599 (15)0.88724 (9)0.0549 (4)
O31.00204 (13)0.70239 (14)0.86708 (8)0.0450 (4)
H3A1.02050.67810.82170.067*
O40.89083 (12)0.78448 (12)0.99533 (7)0.0377 (3)
O50.82812 (16)1.08039 (14)1.03935 (10)0.0603 (4)
H5A0.87531.15321.03850.090*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0359 (9)0.0251 (8)0.0311 (8)−0.0062 (7)0.0024 (7)−0.0044 (7)
C20.0272 (8)0.0273 (8)0.0335 (8)−0.0041 (7)0.0065 (7)0.0005 (7)
C30.0293 (9)0.0290 (9)0.0306 (8)−0.0009 (7)0.0069 (7)−0.0044 (7)
C40.0304 (9)0.0261 (8)0.0297 (8)−0.0029 (7)0.0026 (7)−0.0020 (6)
C50.0500 (11)0.0345 (10)0.0366 (9)−0.0179 (8)0.0149 (8)−0.0064 (8)
C60.0525 (12)0.0372 (10)0.0330 (9)−0.0155 (9)0.0182 (8)−0.0096 (7)
C70.0282 (9)0.0256 (8)0.0294 (8)−0.0014 (7)0.0039 (7)−0.0020 (6)
C80.0319 (9)0.0275 (9)0.0393 (9)−0.0010 (7)0.0008 (7)−0.0103 (7)
C90.0349 (9)0.0257 (9)0.0383 (9)−0.0058 (7)0.0001 (7)−0.0077 (7)
C100.0427 (12)0.0354 (11)0.0864 (16)0.0029 (9)0.0069 (11)−0.0212 (10)
C110.0516 (12)0.0604 (13)0.0370 (10)−0.0061 (10)0.0010 (9)−0.0106 (9)
C120.0684 (15)0.0405 (11)0.0520 (12)−0.0144 (10)−0.0018 (10)0.0039 (9)
C130.0332 (10)0.0472 (11)0.0619 (12)−0.0073 (9)−0.0003 (9)−0.0173 (10)
C140.0469 (11)0.0383 (10)0.0350 (9)−0.0117 (8)0.0114 (8)−0.0096 (7)
C150.0455 (11)0.0407 (11)0.0397 (9)−0.0105 (9)0.0048 (8)−0.0124 (8)
N10.0261 (7)0.0283 (7)0.0329 (7)−0.0013 (6)0.0037 (6)−0.0048 (6)
N20.0287 (8)0.0308 (8)0.0397 (8)−0.0041 (6)0.0086 (6)−0.0106 (6)
O10.0285 (7)0.0448 (8)0.0504 (7)−0.0046 (5)0.0128 (5)−0.0120 (6)
O20.0346 (7)0.0536 (9)0.0789 (10)−0.0084 (6)0.0227 (7)−0.0303 (7)
O30.0498 (8)0.0398 (7)0.0478 (8)−0.0199 (6)0.0229 (6)−0.0127 (6)
O40.0459 (7)0.0306 (6)0.0380 (7)−0.0130 (5)0.0142 (5)−0.0105 (5)
O50.0572 (9)0.0358 (8)0.0862 (11)−0.0076 (7)−0.0097 (8)−0.0098 (7)
Geometric parameters (Å, °) top
C1—O41.3591 (19)C10—H10B0.9600
C1—C61.377 (2)C10—H10C0.9600
C1—C21.401 (2)C11—H11A0.9600
C2—O31.3607 (19)C11—H11B0.9600
C2—C31.374 (2)C11—H11C0.9600
C3—C41.401 (2)C12—H12A0.9600
C3—H30.9300C12—H12B0.9600
C4—C51.387 (2)C12—H12C0.9600
C4—C71.456 (2)C13—H13A0.9600
C5—C61.383 (2)C13—H13B0.9600
C5—H50.9300C13—H13C0.9600
C6—H60.9300C14—O41.436 (2)
C7—N11.341 (2)C14—C151.494 (2)
C7—N21.357 (2)C14—H14A0.9700
C8—N11.504 (2)C14—H14B0.9700
C8—C101.514 (2)C15—O51.408 (2)
C8—C111.529 (3)C15—H15A0.9700
C8—C91.545 (2)C15—H15B0.9700
C9—N21.496 (2)N1—O11.2893 (17)
C9—C131.517 (2)N2—O21.2753 (18)
C9—C121.521 (3)O3—H3A0.8200
C10—H10A0.9600O5—H5A0.8200
O4—C1—C6125.29 (15)C8—C11—H11A109.5
O4—C1—C2115.46 (14)C8—C11—H11B109.5
C6—C1—C2119.24 (14)H11A—C11—H11B109.5
O3—C2—C3124.08 (14)C8—C11—H11C109.5
O3—C2—C1115.55 (14)H11A—C11—H11C109.5
C3—C2—C1120.37 (14)H11B—C11—H11C109.5
C2—C3—C4120.29 (14)C9—C12—H12A109.5
C2—C3—H3119.9C9—C12—H12B109.5
C4—C3—H3119.9H12A—C12—H12B109.5
C5—C4—C3118.94 (15)C9—C12—H12C109.5
C5—C4—C7119.81 (14)H12A—C12—H12C109.5
C3—C4—C7121.21 (14)H12B—C12—H12C109.5
C6—C5—C4120.59 (15)C9—C13—H13A109.5
C6—C5—H5119.7C9—C13—H13B109.5
C4—C5—H5119.7H13A—C13—H13B109.5
C1—C6—C5120.57 (15)C9—C13—H13C109.5
C1—C6—H6119.7H13A—C13—H13C109.5
C5—C6—H6119.7H13B—C13—H13C109.5
N1—C7—N2107.49 (13)O4—C14—C15108.50 (14)
N1—C7—C4127.28 (14)O4—C14—H14A110.0
N2—C7—C4125.20 (14)C15—C14—H14A110.0
N1—C8—C10110.22 (14)O4—C14—H14B110.0
N1—C8—C11106.28 (14)C15—C14—H14B110.0
C10—C8—C11110.42 (16)H14A—C14—H14B108.4
N1—C8—C9100.34 (12)O5—C15—C14109.76 (15)
C10—C8—C9115.11 (15)O5—C15—H15A109.7
C11—C8—C9113.64 (15)C14—C15—H15A109.7
N2—C9—C13109.74 (14)O5—C15—H15B109.7
N2—C9—C12106.19 (14)C14—C15—H15B109.7
C13—C9—C12110.61 (16)H15A—C15—H15B108.2
N2—C9—C8100.22 (12)O1—N1—C7125.74 (13)
C13—C9—C8114.72 (14)O1—N1—C8121.41 (12)
C12—C9—C8114.44 (15)C7—N1—C8112.56 (13)
C8—C10—H10A109.5O2—N2—C7126.26 (14)
C8—C10—H10B109.5O2—N2—C9121.51 (13)
H10A—C10—H10B109.5C7—N2—C9112.12 (13)
C8—C10—H10C109.5C2—O3—H3A109.5
H10A—C10—H10C109.5C1—O4—C14117.73 (12)
H10B—C10—H10C109.5C15—O5—H5A109.5
O4—C1—C2—O31.4 (2)C11—C8—C9—C12158.75 (15)
C6—C1—C2—O3−179.41 (16)O4—C14—C15—O574.74 (19)
O4—C1—C2—C3−178.96 (15)N2—C7—N1—O1−178.94 (14)
C6—C1—C2—C30.2 (3)C4—C7—N1—O12.8 (3)
O3—C2—C3—C4179.57 (16)N2—C7—N1—C87.18 (18)
C1—C2—C3—C40.0 (2)C4—C7—N1—C8−171.10 (15)
C2—C3—C4—C5−0.2 (2)C10—C8—N1—O142.6 (2)
C2—C3—C4—C7177.74 (15)C11—C8—N1—O1−77.09 (18)
C3—C4—C5—C60.2 (3)C9—C8—N1—O1164.37 (14)
C7—C4—C5—C6−177.73 (16)C10—C8—N1—C7−143.25 (16)
O4—C1—C6—C5178.91 (17)C11—C8—N1—C797.09 (16)
C2—C1—C6—C5−0.2 (3)C9—C8—N1—C7−21.46 (17)
C4—C5—C6—C1−0.1 (3)N1—C7—N2—O2−172.08 (16)
C5—C4—C7—N1−155.39 (17)C4—C7—N2—O26.2 (3)
C3—C4—C7—N126.7 (2)N1—C7—N2—C911.58 (18)
C5—C4—C7—N226.6 (3)C4—C7—N2—C9−170.10 (15)
C3—C4—C7—N2−151.31 (16)C13—C9—N2—O238.3 (2)
N1—C8—C9—N224.92 (14)C12—C9—N2—O2−81.3 (2)
C10—C8—C9—N2143.18 (15)C8—C9—N2—O2159.39 (15)
C11—C8—C9—N2−88.10 (16)C13—C9—N2—C7−145.15 (15)
N1—C8—C9—C13142.35 (15)C12—C9—N2—C795.28 (17)
C10—C8—C9—C13−99.39 (19)C8—C9—N2—C7−24.07 (16)
C11—C8—C9—C1329.3 (2)C6—C1—O4—C144.0 (3)
N1—C8—C9—C12−88.24 (16)C2—C1—O4—C14−176.92 (15)
C10—C8—C9—C1230.0 (2)C15—C14—O4—C1−176.62 (15)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1i0.821.912.678 (2)156
O5—H5A···O3ii0.822.342.993 (2)137
O5—H5A···O4ii0.822.463.111 (2)137
C12—H12A···O5iii0.962.573.410 (3)146
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, −y+2, −z+2; (iii) x, y−1, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1i0.821.912.678 (2)156
O5—H5A···O3ii0.822.342.993 (2)137
O5—H5A···O4ii0.822.463.111 (2)137
C12—H12A···O5iii0.962.573.410 (3)146
Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, −y+2, −z+2; (iii) x, y−1, z.
Acknowledgements top

We thank the Natural Science Foundation of Gansu (grant No. 1107RJZA100) for financial support.

references
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