Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807017503/at2269sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807017503/at2269Isup2.hkl |
CCDC reference: 647583
80% Hydrazine hydrate (4.5 g, 72 mmol, 2.0 equiv.) was added slowly, whilst stirring, to a ethanol solution containing 1,3-bis(2-nitrophenoxy)-2-propanol (3.0 g, 9 mmol), FeCl3.6H2O (0.8 g) and active carbon (1.8 g). The mixture was heated, and stirring for about 2 h. The black residue was removed from the solution by filtration, and then the solvent was removed under reduced pressure. The crude product was purified by column chromatography over silica gel using 20% EtOAc-hexane to afford pure yellow crystals, 1.7 g, in a yield of 69%. Single crystals of (I) suitable for X-ray diffraction were obtained from an ethanol-CH2Cl2 mixture by slow evaporation at room temperature.
The H atoms in hydroxy group were located in a difference Fourier map and refine in their as-found positions relative to O atoms with Uiso(H) = 1.2Ueq(O). Other H atoms were placed in calculated positions with C—H = 0.93–0.97 Å and N—H = 0.86 Å, and refined using a riding model. Uiso(H) = 1.2–1.5Ueq(C,N).
Diamine compounds not only are the materials of preparing dyes, paints, oil dope, but also are the important intermediate of synthesizing Schiff base compounds. Recently, Schiff base metal complexes have been widely investigated for their properties and applications in different fields, such as catalysis (Sabater et al., 2001) and materials chemistry (Lacroix 2001).These compounds anchored covalently to various substrates by hydroxy-functioned represents one of the most interesting issues(Bella et al., 2004). Here, the title compound (I) (1,3-bis(2-aminophenoxy)-2-propanol) was prepared from o-nitrophenol and epichlorohydrin, by etherization and reduction of nitro group.
In the crystal structure of the title compound (I), the two phenyl rings were linked by ethereal chain forming a non-coplanar structure (Fig. 1). Layers are formed by the intermolecular hydrogen bonds, and the aryl rings in different molecules are approximately parallel to each other. The O2 atom of the hydroxy group in (I) form two intermolecular hydrogen bonds with the N1 and N2 atoms of two adjeacent molecules, respectively (Fig. 2). The O2 atom is doubly hydrogen bridged. The N2···O2···N1 angle is about 112°. Thus, the molecular packing is controlled by hydrogen bonding interactions.
For related literature, see: Bella et al. (2004); Lacroix (2001); Sabater et al. (2001).
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C15H18N2O3 | F(000) = 584 |
Mr = 274.31 | Dx = 1.327 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2382 reflections |
a = 14.069 (2) Å | θ = 1.5–25.0° |
b = 5.8636 (9) Å | µ = 0.09 mm−1 |
c = 17.112 (3) Å | T = 293 K |
β = 103.418 (7)° | Prism, yellow |
V = 1373.2 (4) Å3 | 0.21 × 0.17 × 0.14 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2382 independent reflections |
Radiation source: fine-focus sealed tube | 1780 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
φ and ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −16→15 |
Tmin = 0.981, Tmax = 0.987 | k = −6→5 |
9223 measured reflections | l = −20→20 |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0761P)2 + 0.31P] where P = (Fo2 + 2Fc2)/3 |
2382 reflections | (Δ/σ)max < 0.001 |
178 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.44 e Å−3 |
C15H18N2O3 | V = 1373.2 (4) Å3 |
Mr = 274.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.069 (2) Å | µ = 0.09 mm−1 |
b = 5.8636 (9) Å | T = 293 K |
c = 17.112 (3) Å | 0.21 × 0.17 × 0.14 mm |
β = 103.418 (7)° |
Bruker SMART CCD area-detector diffractometer | 2382 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1780 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 0.987 | Rint = 0.024 |
9223 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.47 e Å−3 |
2382 reflections | Δρmin = −0.44 e Å−3 |
178 parameters |
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 | ||
C1 | 0.81149 (16) | −0.0370 (4) | 1.01642 (11) | 0.0407 (5) | |
C2 | 0.74359 (18) | −0.1889 (4) | 1.03225 (13) | 0.0521 (6) | |
H2 | 0.7647 | −0.3147 | 1.0648 | 0.063* | |
C3 | 0.64443 (19) | −0.1577 (5) | 1.00061 (14) | 0.0597 (7) | |
H3 | 0.5997 | −0.2624 | 1.0117 | 0.072* | |
C4 | 0.61236 (18) | 0.0277 (5) | 0.95297 (15) | 0.0618 (7) | |
H4 | 0.5458 | 0.0506 | 0.9328 | 0.074* | |
C5 | 0.67907 (16) | 0.1809 (4) | 0.93479 (13) | 0.0518 (6) | |
H5 | 0.6573 | 0.3060 | 0.9021 | 0.062* | |
C6 | 0.77767 (14) | 0.1480 (4) | 0.96517 (11) | 0.0385 (5) | |
C7 | 0.82321 (10) | 0.4514 (2) | 0.88735 (8) | 0.0396 (5) | |
H7A | 0.7834 | 0.5690 | 0.9037 | 0.048* | |
H7B | 0.7856 | 0.3803 | 0.8388 | 0.048* | |
C8 | 0.91478 (10) | 0.5536 (2) | 0.87210 (8) | 0.0372 (5) | |
H8 | 0.9573 | 0.5919 | 0.9244 | 0.045* | |
C9 | 0.89298 (15) | 0.7733 (3) | 0.82454 (12) | 0.0405 (5) | |
H9A | 0.8643 | 0.8836 | 0.8545 | 0.049* | |
H9B | 0.9530 | 0.8371 | 0.8153 | 0.049* | |
C10 | 0.74699 (14) | 0.8723 (3) | 0.72770 (11) | 0.0354 (5) | |
C11 | 0.65635 (15) | 0.7980 (4) | 0.73339 (13) | 0.0492 (6) | |
H11 | 0.6497 | 0.6563 | 0.7560 | 0.059* | |
C12 | 0.57499 (18) | 0.9325 (5) | 0.70570 (15) | 0.0610 (7) | |
H12 | 0.5135 | 0.8825 | 0.7096 | 0.073* | |
C13 | 0.58582 (18) | 1.1407 (5) | 0.67236 (14) | 0.0604 (7) | |
H13 | 0.5312 | 1.2317 | 0.6532 | 0.072* | |
C14 | 0.67606 (17) | 1.2160 (4) | 0.66696 (13) | 0.0512 (6) | |
H14 | 0.6819 | 1.3580 | 0.6443 | 0.061* | |
C15 | 0.75904 (14) | 1.0847 (3) | 0.69467 (10) | 0.0364 (5) | |
N1 | 0.91044 (15) | −0.0606 (4) | 1.04645 (13) | 0.0733 (7) | |
H1A | 0.9328 | −0.1746 | 1.0768 | 0.088* | |
H1B | 0.9500 | 0.0387 | 1.0349 | 0.088* | |
N2 | 0.85195 (13) | 1.1623 (3) | 0.69122 (10) | 0.0459 (5) | |
H2A | 0.8587 | 1.2946 | 0.6715 | 0.055* | |
H2B | 0.9023 | 1.0777 | 0.7088 | 0.055* | |
O1 | 0.85053 (10) | 0.2843 (2) | 0.94980 (8) | 0.0464 (4) | |
O2 | 0.96575 (9) | 0.3940 (2) | 0.83438 (8) | 0.0430 (4) | |
H2C | 1.0155 | 0.4535 | 0.8266 | 0.064* | |
O3 | 0.82630 (10) | 0.7260 (2) | 0.74908 (7) | 0.0414 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0495 (13) | 0.0407 (13) | 0.0340 (10) | −0.0012 (10) | 0.0137 (9) | 0.0010 (9) |
C2 | 0.0749 (17) | 0.0417 (14) | 0.0452 (12) | −0.0087 (12) | 0.0248 (12) | 0.0035 (10) |
C3 | 0.0668 (17) | 0.0579 (17) | 0.0619 (14) | −0.0267 (14) | 0.0298 (13) | −0.0086 (13) |
C4 | 0.0450 (14) | 0.0731 (19) | 0.0681 (15) | −0.0120 (13) | 0.0150 (12) | −0.0047 (14) |
C5 | 0.0443 (13) | 0.0573 (15) | 0.0519 (12) | −0.0022 (12) | 0.0075 (10) | 0.0082 (12) |
C6 | 0.0424 (12) | 0.0379 (12) | 0.0360 (10) | −0.0050 (10) | 0.0108 (9) | 0.0008 (9) |
C7 | 0.0431 (12) | 0.0365 (12) | 0.0385 (10) | 0.0043 (10) | 0.0079 (9) | 0.0070 (9) |
C8 | 0.0389 (11) | 0.0347 (12) | 0.0382 (10) | 0.0043 (9) | 0.0092 (9) | 0.0035 (9) |
C9 | 0.0442 (12) | 0.0311 (11) | 0.0438 (11) | −0.0009 (9) | 0.0054 (9) | 0.0027 (9) |
C10 | 0.0387 (12) | 0.0322 (12) | 0.0347 (10) | 0.0055 (9) | 0.0075 (8) | 0.0007 (9) |
C11 | 0.0464 (14) | 0.0485 (14) | 0.0538 (12) | 0.0002 (11) | 0.0140 (10) | 0.0070 (11) |
C12 | 0.0404 (13) | 0.0744 (19) | 0.0682 (15) | 0.0035 (13) | 0.0123 (11) | 0.0030 (14) |
C13 | 0.0481 (15) | 0.0671 (18) | 0.0634 (15) | 0.0233 (13) | 0.0076 (12) | 0.0076 (14) |
C14 | 0.0601 (15) | 0.0419 (14) | 0.0504 (13) | 0.0144 (12) | 0.0104 (11) | 0.0104 (10) |
C15 | 0.0429 (12) | 0.0341 (12) | 0.0328 (9) | 0.0045 (10) | 0.0103 (8) | 0.0014 (9) |
N1 | 0.0546 (13) | 0.0726 (16) | 0.0848 (15) | 0.0004 (11) | −0.0002 (11) | 0.0421 (13) |
N2 | 0.0504 (11) | 0.0350 (11) | 0.0530 (10) | 0.0024 (9) | 0.0136 (8) | 0.0103 (8) |
O1 | 0.0404 (8) | 0.0469 (9) | 0.0497 (8) | −0.0050 (7) | 0.0062 (7) | 0.0189 (7) |
O2 | 0.0381 (8) | 0.0388 (9) | 0.0551 (8) | 0.0061 (7) | 0.0169 (6) | 0.0065 (7) |
O3 | 0.0465 (9) | 0.0337 (8) | 0.0413 (8) | 0.0091 (7) | 0.0049 (6) | 0.0019 (6) |
C1—N1 | 1.375 (3) | C9—H9A | 0.9700 |
C1—C2 | 1.378 (3) | C9—H9B | 0.9700 |
C1—C6 | 1.407 (3) | C10—C11 | 1.372 (3) |
C2—C3 | 1.387 (3) | C10—O3 | 1.388 (2) |
C2—H2 | 0.9300 | C10—C15 | 1.394 (3) |
C3—C4 | 1.371 (4) | C11—C12 | 1.380 (3) |
C3—H3 | 0.9300 | C11—H11 | 0.9300 |
C4—C5 | 1.386 (3) | C12—C13 | 1.371 (4) |
C4—H4 | 0.9300 | C12—H12 | 0.9300 |
C5—C6 | 1.377 (3) | C13—C14 | 1.367 (3) |
C5—H5 | 0.9300 | C13—H13 | 0.9300 |
C6—O1 | 1.373 (2) | C14—C15 | 1.387 (3) |
C7—O1 | 1.4350 (19) | C14—H14 | 0.9300 |
C7—C8 | 1.4978 | C15—N2 | 1.398 (3) |
C7—H7A | 0.9700 | N1—H1A | 0.8600 |
C7—H7B | 0.9700 | N1—H1B | 0.8600 |
C8—O2 | 1.422 (2) | N2—H2A | 0.8600 |
C8—C9 | 1.516 (2) | N2—H2B | 0.8600 |
C8—H8 | 0.9800 | O2—H2C | 0.8200 |
C9—O3 | 1.436 (2) | ||
N1—C1—C2 | 123.3 (2) | C8—C9—H9A | 109.9 |
N1—C1—C6 | 118.52 (19) | O3—C9—H9B | 109.9 |
C2—C1—C6 | 118.1 (2) | C8—C9—H9B | 109.9 |
C1—C2—C3 | 121.2 (2) | H9A—C9—H9B | 108.3 |
C1—C2—H2 | 119.4 | C11—C10—O3 | 119.26 (19) |
C3—C2—H2 | 119.4 | C11—C10—C15 | 120.98 (19) |
C4—C3—C2 | 120.0 (2) | O3—C10—C15 | 119.54 (17) |
C4—C3—H3 | 120.0 | C10—C11—C12 | 120.3 (2) |
C2—C3—H3 | 120.0 | C10—C11—H11 | 119.9 |
C3—C4—C5 | 120.1 (2) | C12—C11—H11 | 119.9 |
C3—C4—H4 | 120.0 | C13—C12—C11 | 119.2 (2) |
C5—C4—H4 | 120.0 | C13—C12—H12 | 120.4 |
C6—C5—C4 | 120.0 (2) | C11—C12—H12 | 120.4 |
C6—C5—H5 | 120.0 | C14—C13—C12 | 120.7 (2) |
C4—C5—H5 | 120.0 | C14—C13—H13 | 119.7 |
O1—C6—C5 | 125.27 (19) | C12—C13—H13 | 119.7 |
O1—C6—C1 | 114.13 (17) | C13—C14—C15 | 121.2 (2) |
C5—C6—C1 | 120.6 (2) | C13—C14—H14 | 119.4 |
O1—C7—C8 | 108.08 (8) | C15—C14—H14 | 119.4 |
O1—C7—H7A | 110.1 | C14—C15—C10 | 117.6 (2) |
C8—C7—H7A | 110.1 | C14—C15—N2 | 121.7 (2) |
O1—C7—H7B | 110.1 | C10—C15—N2 | 120.70 (17) |
C8—C7—H7B | 110.1 | C1—N1—H1A | 120.0 |
H7A—C7—H7B | 108.4 | C1—N1—H1B | 120.0 |
O2—C8—C7 | 111.14 (8) | H1A—N1—H1B | 120.0 |
O2—C8—C9 | 112.07 (13) | C15—N2—H2A | 120.0 |
C7—C8—C9 | 110.99 (10) | C15—N2—H2B | 120.0 |
O2—C8—H8 | 107.5 | H2A—N2—H2B | 120.0 |
C7—C8—H8 | 107.5 | C6—O1—C7 | 117.22 (13) |
C9—C8—H8 | 107.5 | C8—O2—H2C | 109.5 |
O3—C9—C8 | 109.11 (15) | C10—O3—C9 | 115.81 (15) |
O3—C9—H9A | 109.9 | ||
N1—C1—C2—C3 | 179.9 (2) | C15—C10—C11—C12 | 0.5 (3) |
C6—C1—C2—C3 | −1.8 (3) | C10—C11—C12—C13 | 0.1 (4) |
C1—C2—C3—C4 | −0.3 (4) | C11—C12—C13—C14 | −0.5 (4) |
C2—C3—C4—C5 | 1.6 (4) | C12—C13—C14—C15 | 0.2 (4) |
C3—C4—C5—C6 | −0.5 (4) | C13—C14—C15—C10 | 0.5 (3) |
C4—C5—C6—O1 | 178.3 (2) | C13—C14—C15—N2 | −178.43 (19) |
C4—C5—C6—C1 | −1.7 (3) | C11—C10—C15—C14 | −0.8 (3) |
N1—C1—C6—O1 | 1.2 (3) | O3—C10—C15—C14 | 173.84 (17) |
C2—C1—C6—O1 | −177.11 (17) | C11—C10—C15—N2 | 178.09 (18) |
N1—C1—C6—C5 | −178.8 (2) | O3—C10—C15—N2 | −7.3 (3) |
C2—C1—C6—C5 | 2.9 (3) | C5—C6—O1—C7 | −10.7 (3) |
O1—C7—C8—O2 | 70.28 (11) | C1—C6—O1—C7 | 169.24 (16) |
O1—C7—C8—C9 | −164.28 (16) | C8—C7—O1—C6 | −171.17 (12) |
O2—C8—C9—O3 | 65.35 (19) | C11—C10—O3—C9 | −105.4 (2) |
C7—C8—C9—O3 | −59.57 (16) | C15—C10—O3—C9 | 79.9 (2) |
O3—C10—C11—C12 | −174.1 (2) | C8—C9—O3—C10 | 132.46 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 2.24 | 3.061 (2) | 161 |
N1—H1B···N1i | 0.86 | 2.66 | 3.353 (4) | 139 |
N2—H2B···O2ii | 0.86 | 2.41 | 3.125 (2) | 142 |
O2—H2C···N2iii | 0.82 | 2.31 | 3.125 (2) | 173 |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C15H18N2O3 |
Mr | 274.31 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 14.069 (2), 5.8636 (9), 17.112 (3) |
β (°) | 103.418 (7) |
V (Å3) | 1373.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.21 × 0.17 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.981, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9223, 2382, 1780 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.146, 1.10 |
No. of reflections | 2382 |
No. of parameters | 178 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.44 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2i | 0.86 | 2.24 | 3.061 (2) | 160.7 |
N1—H1B···N1i | 0.86 | 2.66 | 3.353 (4) | 138.5 |
N2—H2B···O2ii | 0.86 | 2.41 | 3.125 (2) | 141.5 |
O2—H2C···N2iii | 0.82 | 2.31 | 3.125 (2) | 173.1 |
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+2, y+1/2, −z+3/2; (iii) −x+2, y−1/2, −z+3/2. |
Diamine compounds not only are the materials of preparing dyes, paints, oil dope, but also are the important intermediate of synthesizing Schiff base compounds. Recently, Schiff base metal complexes have been widely investigated for their properties and applications in different fields, such as catalysis (Sabater et al., 2001) and materials chemistry (Lacroix 2001).These compounds anchored covalently to various substrates by hydroxy-functioned represents one of the most interesting issues(Bella et al., 2004). Here, the title compound (I) (1,3-bis(2-aminophenoxy)-2-propanol) was prepared from o-nitrophenol and epichlorohydrin, by etherization and reduction of nitro group.
In the crystal structure of the title compound (I), the two phenyl rings were linked by ethereal chain forming a non-coplanar structure (Fig. 1). Layers are formed by the intermolecular hydrogen bonds, and the aryl rings in different molecules are approximately parallel to each other. The O2 atom of the hydroxy group in (I) form two intermolecular hydrogen bonds with the N1 and N2 atoms of two adjeacent molecules, respectively (Fig. 2). The O2 atom is doubly hydrogen bridged. The N2···O2···N1 angle is about 112°. Thus, the molecular packing is controlled by hydrogen bonding interactions.