supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, o3701    [ doi:10.1107/S1600536807037397 ]

N-[2-(4-Hydroxybenzylideneamino)ethyl]-N-[2-(4-oxidobenzylideneamino)ethyl]ammonium

X.-M. Tian, G. Liu, Y. Feng and J.-D. Wang

Abstract top

The title Schiff base compound, C18H21N3O2, was synthesized by a condensation reaction of 4-hydroxybenzaldehyde with diethylenetriamine. The crystal structure determination reveals that one of the terminal hydroxy groups is deprotonated while the imino group of the molecule is protonated; thus the compound is a zwitterion. The two terminal benzene rings are nearly parallel to one another, with a dihedral angle of 9.94 (6)°. Intermolecular O-H...O and N-H...O hydrogen bonding helps to stabilize the crystal structure.

Comment top

Schiff bases are important organic compounds and their metal complexes had a variety of applications including biological, clinical, analytical and catalysis (Mohamed, 2006; Jiao & Liu, 2005). In particular, Schiff bases with nitrogen and oxygen atoms are important biological ligands (Li et al., 1999). Some Schiff base cobalt complexes can absorb molecular oxygen, they were synthesized as functional model compounds to simulate a biological oxygen carrier (Xiao et al., 1987). In our lab, the oxygenation of some cobalt complexes with Schiff bases have been investigated, and found that one molar of the complexes reacted with two molar of oxygen at room temperature (Xiao et al., 2006). As part of our ongoing investigation, the title compound has been prepared and its crystal structure is reported here.

The molecule forms a U type structure (Fig. 1). The bond lengths of N1═C7 and N3═C12 (Table 1) indicate double bonds character. The C1-benzene ring is nearly parallel to the C13-benzene ring, the dihedral angle being 9.94 (6)°. The protonation of N2-imine group make the compound crystallize in a zwitterionic form. The crystal structure is stabilized by O—H···O hydrogen bonding (Table 2).

Related literature top

For general background, see: Mohamed (2006); Jiao & Liu (2005); Li et al. (1999); Xiao et al. (2006 or??1987). For synthesis, see: Xiao et al. (2006).

Experimental top

diethylenetriamine(0.103 g, 0.001 mol) in ethyl acetate (10 ml) was dropwised to a solution of 4-hydroxybenzaldehyde (0.244 g, 0.002 mol) in ethyl acetate (20 ml) in an ice-bath, then the reaction mixture was stirred for two hours, The yellow product was isolated by filtration, washed with diethyl ether, dried and obtained 0.264 g (yield 85%) (Xiao et al., 2006). Crystals suitable for single-crystal X-ray diffraction were grown from a solution of methanol by slow evaporation. Elemental analysis, found (calculated for C18H21N3O2): C 69.18% (69.45%), H 6.51% (6.75%), N 13.45% (13.50%).

Refinement top

H atoms bonded to O and N atoms were located in a difference Fourier map and refined as riding in as-found relative positions with Uiso(H) = 1.5Ueq(O,N). Other H atoms were placed in calculated positions with C—H = 0.95 (aromatic) or 0.99 Å (methylene), and refined in riding mode, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of the molecule structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
N-[2-(4-hydroxybenzylideneamino)ethyl]-N-[2-(4- oxidobenzylideneamino)ethyl]ammonium top
Crystal data top
C18H21N3O2Dx = 1.333 Mg m−3
Mr = 311.38Melting point: 453 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 23448 reflections
a = 11.638 (2) Åθ = 3.2–27.5°
b = 15.667 (3) ŵ = 0.09 mm−1
c = 17.016 (3) ÅT = 153 K
V = 3102.5 (11) Å3Block, yellow
Z = 80.49 × 0.47 × 0.38 mm
F(000) = 1328
Data collection top
Rigaku R-AXIS SPIDER
diffractometer		3084 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.023
graphiteθmax = 27.5°, θmin = 3.2°
ω scansh = −15→15
28871 measured reflectionsk = −19→20
3560 independent reflectionsl = −20→22
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.097P)2 + 1.4677P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.036(Δ/σ)max = 0.001
wR(F2) = 0.112Δρmax = 0.32 e Å−3
S = 1.06Δρmin = −0.24 e Å−3
3560 reflectionsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
209 parametersExtinction coefficient: 0.0026 (6)
0 restraints
Crystal data top
C18H21N3O2V = 3102.5 (11) Å3
Mr = 311.38Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 11.638 (2) ŵ = 0.09 mm−1
b = 15.667 (3) ÅT = 153 K
c = 17.016 (3) Å0.49 × 0.47 × 0.38 mm
Data collection top
Rigaku R-AXIS SPIDER
diffractometer		Rint = 0.023
28871 measured reflectionsθmax = 27.5°
3560 independent reflectionsStandard reflections: 0
3084 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.112Δρmax = 0.32 e Å−3
S = 1.06Δρmin = −0.24 e Å−3
3560 reflectionsAbsolute structure: ?
209 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
O10.31037 (6)0.14542 (5)0.55715 (4)0.02288 (18)
H1A0.36620.13960.51480.034*
O20.94930 (6)0.35847 (5)0.55366 (4)0.02240 (18)
N10.47454 (7)0.12911 (5)0.91717 (5)0.02032 (19)
N20.62800 (6)0.25607 (5)0.98495 (5)0.01873 (19)
H2A0.67780.22630.95340.028*
H2C0.57800.28620.95600.028*
N30.79044 (7)0.37646 (5)0.91501 (5)0.02038 (19)
C10.35115 (9)0.14906 (6)0.76874 (6)0.0209 (2)
H1B0.31240.16970.81400.025*
C20.30268 (9)0.16082 (6)0.69552 (6)0.0210 (2)
H2B0.23090.18930.69100.025*
C30.35837 (8)0.13108 (6)0.62770 (5)0.0180 (2)
C40.46222 (8)0.08697 (6)0.63589 (5)0.0191 (2)
H4A0.49980.06460.59080.023*
C50.51049 (9)0.07584 (6)0.70980 (6)0.0193 (2)
H5A0.58150.04640.71460.023*
C60.45656 (8)0.10712 (6)0.77718 (5)0.0182 (2)
C70.51216 (8)0.09588 (6)0.85382 (6)0.0188 (2)
H7A0.57980.06200.85640.023*
C80.53900 (9)0.11116 (6)0.98880 (5)0.0198 (2)
H8A0.61240.08290.97510.024*
H8B0.49430.07171.02240.024*
C90.56376 (8)0.19273 (6)1.03400 (5)0.0183 (2)
H9A0.49030.21841.05150.022*
H9B0.60950.17891.08140.022*
C100.69938 (8)0.31620 (6)1.03268 (5)0.0187 (2)
H10A0.77170.28761.04820.022*
H10B0.65730.33161.08120.022*
C110.72732 (9)0.39669 (6)0.98682 (5)0.0203 (2)
H11A0.65510.42670.97310.024*
H11B0.77400.43531.01990.024*
C120.75025 (8)0.40705 (6)0.85139 (6)0.0188 (2)
H12A0.68150.43960.85390.023*
C130.80451 (8)0.39474 (6)0.77449 (5)0.0178 (2)
C140.74795 (8)0.42303 (6)0.70696 (5)0.0192 (2)
H14A0.67530.45030.71170.023*
C150.79631 (9)0.41193 (6)0.63302 (5)0.0190 (2)
H15A0.75670.43220.58790.023*
C160.90284 (9)0.37112 (6)0.62407 (5)0.0176 (2)
C170.96003 (8)0.34366 (6)0.69268 (6)0.0203 (2)
H17A1.03290.31670.68840.024*
C180.91180 (9)0.35543 (6)0.76583 (6)0.0200 (2)
H18A0.95210.33650.81120.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0195 (4)0.0323 (4)0.0168 (3)0.0039 (3)−0.0027 (3)0.0013 (3)
O20.0206 (4)0.0307 (4)0.0159 (3)0.0027 (3)0.0029 (3)−0.0011 (3)
N10.0177 (4)0.0252 (4)0.0180 (4)−0.0004 (3)−0.0020 (3)0.0003 (3)
N20.0175 (4)0.0252 (4)0.0136 (4)−0.0030 (3)−0.0001 (3)−0.0005 (3)
N30.0179 (4)0.0251 (4)0.0182 (4)−0.0013 (3)0.0031 (3)−0.0019 (3)
C10.0186 (5)0.0251 (5)0.0188 (5)0.0013 (4)0.0020 (3)−0.0028 (4)
C20.0164 (5)0.0244 (5)0.0221 (5)0.0033 (4)−0.0006 (3)−0.0014 (4)
C30.0171 (5)0.0189 (4)0.0179 (4)−0.0029 (3)−0.0012 (3)0.0010 (3)
C40.0184 (5)0.0215 (5)0.0173 (4)0.0004 (4)0.0019 (3)−0.0007 (3)
C50.0167 (5)0.0203 (4)0.0210 (5)0.0022 (4)0.0006 (3)0.0005 (3)
C60.0179 (5)0.0190 (4)0.0178 (4)−0.0018 (3)−0.0007 (3)0.0006 (3)
C70.0168 (5)0.0198 (4)0.0199 (5)−0.0005 (3)−0.0006 (3)0.0012 (3)
C80.0185 (5)0.0222 (5)0.0187 (4)0.0003 (4)−0.0017 (3)0.0014 (4)
C90.0172 (5)0.0238 (5)0.0139 (4)−0.0006 (4)0.0008 (3)0.0016 (3)
C100.0165 (5)0.0255 (5)0.0140 (4)−0.0014 (4)−0.0006 (3)−0.0028 (3)
C110.0190 (5)0.0232 (5)0.0188 (5)−0.0004 (4)0.0030 (3)−0.0034 (4)
C120.0167 (5)0.0189 (4)0.0208 (5)−0.0011 (3)0.0022 (3)−0.0019 (3)
C130.0176 (5)0.0180 (4)0.0178 (5)−0.0018 (3)0.0017 (3)−0.0006 (3)
C140.0161 (5)0.0197 (4)0.0219 (5)0.0013 (3)−0.0004 (4)−0.0006 (4)
C150.0188 (5)0.0210 (4)0.0171 (4)−0.0002 (4)−0.0030 (3)0.0010 (3)
C160.0182 (5)0.0183 (4)0.0164 (4)−0.0032 (3)0.0011 (3)−0.0009 (3)
C170.0155 (5)0.0242 (5)0.0211 (5)0.0028 (4)0.0005 (3)0.0007 (4)
C180.0183 (5)0.0242 (5)0.0175 (4)0.0008 (4)−0.0011 (3)0.0019 (3)
Geometric parameters (Å, °) top
O1—C31.3430 (11)C8—C91.5192 (13)
O1—H1A0.9745C8—H8A0.9900
O2—C161.3293 (11)C8—H8B0.9900
N1—C71.2747 (13)C9—H9A0.9900
N1—C81.4586 (12)C9—H9B0.9900
N2—C101.4957 (12)C10—C111.5183 (14)
N2—C91.4968 (12)C10—H10A0.9900
N2—H2A0.9170C10—H10B0.9900
N2—H2C0.8972C11—H11A0.9900
N3—C121.2730 (13)C11—H11B0.9900
N3—C111.4605 (12)C12—C131.4656 (13)
C1—C21.3801 (14)C12—H12A0.9500
C1—C61.3990 (14)C13—C141.3965 (13)
C1—H1B0.9500C13—C181.4000 (14)
C2—C31.4031 (13)C14—C151.3892 (13)
C2—H2B0.9500C14—H14A0.9500
C3—C41.3992 (14)C15—C161.4032 (14)
C4—C51.3883 (13)C15—H15A0.9500
C4—H4A0.9500C16—C171.4111 (13)
C5—C61.3959 (13)C17—C181.3778 (13)
C5—H5A0.9500C17—H17A0.9500
C6—C71.4666 (13)C18—H18A0.9500
C7—H7A0.9500
C3—O1—H1A111.6C8—C9—H9A109.3
C7—N1—C8116.82 (9)N2—C9—H9B109.3
C10—N2—C9113.08 (7)C8—C9—H9B109.3
C10—N2—H2A106.7H9A—C9—H9B107.9
C9—N2—H2A107.8N2—C10—C11111.28 (7)
C10—N2—H2C109.1N2—C10—H10A109.4
C9—N2—H2C109.3C11—C10—H10A109.4
H2A—N2—H2C110.8N2—C10—H10B109.4
C12—N3—C11116.42 (9)C11—C10—H10B109.4
C2—C1—C6120.91 (9)H10A—C10—H10B108.0
C2—C1—H1B119.5N3—C11—C10110.95 (8)
C6—C1—H1B119.5N3—C11—H11A109.4
C1—C2—C3120.63 (9)C10—C11—H11A109.4
C1—C2—H2B119.7N3—C11—H11B109.4
C3—C2—H2B119.7C10—C11—H11B109.4
O1—C3—C4122.06 (9)H11A—C11—H11B108.0
O1—C3—C2119.18 (9)N3—C12—C13123.46 (9)
C4—C3—C2118.75 (9)N3—C12—H12A118.3
C5—C4—C3120.11 (9)C13—C12—H12A118.3
C5—C4—H4A119.9C14—C13—C18118.25 (8)
C3—C4—H4A119.9C14—C13—C12119.33 (9)
C4—C5—C6121.20 (9)C18—C13—C12122.42 (9)
C4—C5—H5A119.4C15—C14—C13120.97 (9)
C6—C5—H5A119.4C15—C14—H14A119.5
C5—C6—C1118.35 (9)C13—C14—H14A119.5
C5—C6—C7119.34 (9)C14—C15—C16120.88 (9)
C1—C6—C7122.31 (9)C14—C15—H15A119.6
N1—C7—C6123.47 (9)C16—C15—H15A119.6
N1—C7—H7A118.3O2—C16—C15121.68 (8)
C6—C7—H7A118.3O2—C16—C17120.56 (9)
N1—C8—C9111.00 (8)C15—C16—C17117.76 (8)
N1—C8—H8A109.4C18—C17—C16120.96 (9)
C9—C8—H8A109.4C18—C17—H17A119.5
N1—C8—H8B109.4C16—C17—H17A119.5
C9—C8—H8B109.4C17—C18—C13121.15 (9)
H8A—C8—H8B108.0C17—C18—H18A119.4
N2—C9—C8111.72 (7)C13—C18—H18A119.4
N2—C9—H9A109.3
C6—C1—C2—C3−0.18 (16)C9—N2—C10—C11−159.33 (8)
C1—C2—C3—O1−178.33 (9)C12—N3—C11—C10127.76 (9)
C1—C2—C3—C41.95 (15)N2—C10—C11—N3−59.52 (10)
O1—C3—C4—C5178.05 (9)C11—N3—C12—C13178.42 (8)
C2—C3—C4—C5−2.24 (14)N3—C12—C13—C14173.33 (9)
C3—C4—C5—C60.78 (15)N3—C12—C13—C18−6.70 (15)
C4—C5—C6—C10.99 (14)C18—C13—C14—C150.49 (14)
C4—C5—C6—C7−178.39 (9)C12—C13—C14—C15−179.54 (9)
C2—C1—C6—C5−1.29 (15)C13—C14—C15—C160.70 (15)
C2—C1—C6—C7178.07 (9)C14—C15—C16—O2178.66 (9)
C8—N1—C7—C6179.39 (8)C14—C15—C16—C17−1.43 (14)
C5—C6—C7—N1173.30 (9)O2—C16—C17—C18−179.09 (9)
C1—C6—C7—N1−6.06 (15)C15—C16—C17—C181.00 (14)
C7—N1—C8—C9130.85 (9)C16—C17—C18—C130.18 (15)
C10—N2—C9—C8−153.53 (8)C14—C13—C18—C17−0.93 (14)
N1—C8—C9—N2−57.22 (10)C12—C13—C18—C17179.10 (9)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O2i0.971.512.4846 (11)173
N2—H2A···O1ii0.922.002.8325 (12)149
N2—H2C···O2iii0.901.882.7075 (12)152
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, y, −z+3/2; (iii) x−1/2, y, −z+3/2.
Table 1
Selected geometric parameters (Å) top
O1—C31.3430 (11)N1—C71.2747 (13)
O2—C161.3293 (11)N3—C121.2730 (13)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O2i0.971.512.4846 (11)173
N2—H2A···O1ii0.922.002.8325 (12)149
N2—H2C···O2iii0.901.882.7075 (12)152
Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, y, −z+3/2; (iii) x−1/2, y, −z+3/2.
Acknowledgements top

We gratefully acknowledge financial support from the National Natural Science Foundation of China (Nos. 20461003 and 20562011), the Program for New Century Excellent Talents in Universities (NCET-04–0987) and the Specialized Research Fund for the Doctoral Program of Higher Education (No. 200507550033).

references
References top

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Jiao, T.-F. & Liu, M.-H. (2005). J. Phys. Chem. B, 109, 2532–2539.

Li, J.-Z., Qin, S.-Y. & Li, Z.-H. (1999). Acta Chim. Sinica, 57, 298–304.

Mohamed, G. G. (2006). Spectrochim. Acta Part A, 64, 188–195.

Rigaku (2004). RAPID-AUTO. Version 3.0. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2004). CrystalStructure. Version 3.7.0. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Xiao, F.-R., Wang, J.-D., Yue, F., Wu, R.-L. & Li, J. (2006). Acta Chim. Sinica, 64, 1517–1522. Please check date; 1987 in Related literature section and in Comment section in CIF