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Acta Cryst. (2008). E64, o2110    [ doi:10.1107/S1600536808032406 ]

4-[3-(4-Nitrophenoxy)propoxy]aniline

L.-M. Zheng, X. Wei, X.-R. Peng, J.-P. Zeng and Y.-Q. Zhang

Abstract top

The molecules of the title compound, C15H16N2O4, are linked via N-H...O hydrogen bonds, forming undulating one-dimensional chains. Adjacent chains are linked by weak C-H...[pi] interactions, forming a three-dimensional network.

Comment top

As part of our ongoing investigation on bibenzene compound, we present the crystal structure of the title compound (I) containing multiple functional groups that can develop strong interactions with cucurbit[n]urils (CB[n]) (Freeman et al., 1981; Day & Arnold, 2000; Day et al., 2002; Kim et al., 2000)

The crystal structure of (I) is shown in Fig.1. Two phenyl rings were linked by ethereal chain forming a non-coplanar structure and the dihedral angle between two phenyl ring is 26.13 (9) Å. Molecules are linked via N2—H2B···O1 hydrogen bonds forming a undulant one-dimensional chains (Fig. 2) and adjacent chains are linked by C—H···π interaction forming a three-dimensional framework (Table 1, Cg1 and Cg2 are centroids of the phenyl ring (C1—C6) and (C10—C15), respectively).

Related literature top

For general background, see: Day & Arnold (2000); Day et al. (2002); Freeman et al. (1981); Kim et al. (2000). Cg1 and Cg2 are the centroids of the C1–C6 and C10–C15 phenyl rings, respectively

Experimental top

P-toluenesulfonyl chloride (7.62 g, 40 mmol) was added slowly, whilst stirring, to a pyridine solution (50 ml) containing 1,3-propanediol (1.52 g, 20 mmol). The mixture was stirred for about 4 h in the range of 268 K - 278 K. Water (40 ml) was added to the resulting solution, the precipitate was collected by filtration, the solid product was crystallized using ethanol. The solid product (6.85 g, 20 mmol) dissolved in DMF (100 ml) containing K2CO3 (2 g), p-nitrophenol (0.54 g, 4 mmol) was added slowly, to the DMF(100 ml) solution, and the mixture was heated at 353 K for 24 h, and then the solvent was removed into water and filtered, the residue was washed with water, and 1,3-bis(-nitrylphenoxy)-propane was obtained. Hydrazine (30 g,80%) was added slowly to a stirred solution of ethanol (50 ml) containing 1,4-bis(-nitrylphenoxy)-propane (3.12 g, 10 mmol), FeCl3.6H2O (0.8 g) and active carbon (1.8 g) at 348 K for 5 h, and then the solvent was filtered, the solid product was crystallized using ethanol, Single crystals of (I) were obtained after a week.

Refinement top

All H atoms were placed in calculated positions and refined as riding, with C—H = 0.97 Å (methylene) and 0.93 Å (aromatic), N—H = 0.861 Å, and Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Packing diagram of (I). Hydrogen bonds are shown as dashed lines.
4-[3-(4-Nitrophenoxy)propoxy]aniline top
Crystal data top
C15H16N2O4F(000) = 1216
Mr = 288.30Dx = 1.341 Mg m−3
Orthorhombic, PccnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 2509 reflections
a = 10.808 (8) Åθ = 2.0–25.0°
b = 34.79 (3) ŵ = 0.10 mm−1
c = 7.596 (6) ÅT = 298 K
V = 2857 (4) Å3Prism, brown
Z = 80.23 × 0.19 × 0.16 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2509 independent reflections
Radiation source: fine-focus sealed tube1554 reflections with I > 2σ(I)
graphiteRint = 0.065
φ and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		h = −12→12
Tmin = 0.978, Tmax = 0.984k = −37→41
17736 measured reflectionsl = −8→9
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0596P)2]
where P = (Fo2 + 2Fc2)/3
2509 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.25 e Å−3
0 restraintsΔρmin = −0.16 e Å−3
Crystal data top
C15H16N2O4V = 2857 (4) Å3
Mr = 288.30Z = 8
Orthorhombic, PccnMo Kα radiation
a = 10.808 (8) ŵ = 0.10 mm−1
b = 34.79 (3) ÅT = 298 K
c = 7.596 (6) Å0.23 × 0.19 × 0.16 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2509 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)		1554 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.984Rint = 0.065
17736 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.126Δρmax = 0.25 e Å−3
S = 1.05Δρmin = −0.16 e Å−3
2509 reflectionsAbsolute structure: ?
190 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
C10.3694 (2)0.52612 (6)0.2758 (3)0.0531 (6)
C20.4692 (2)0.54418 (6)0.1976 (3)0.0587 (6)
H20.54270.53080.17930.070*
C30.2592 (2)0.54512 (6)0.3021 (3)0.0575 (6)
H30.19260.53260.35410.069*
C40.4590 (2)0.58237 (6)0.1467 (3)0.0528 (6)
H40.52590.59490.09500.063*
C50.2486 (2)0.58278 (6)0.2507 (3)0.0556 (6)
H50.17430.59570.26760.067*
C60.3483 (2)0.60180 (6)0.1735 (3)0.0468 (5)
C70.4269 (2)0.66196 (6)0.0598 (3)0.0540 (6)
H7A0.44870.6531−0.05710.065*
H7B0.49940.66000.13460.065*
C80.3816 (2)0.70308 (6)0.0527 (3)0.0577 (6)
H8A0.31020.7046−0.02440.069*
H8B0.35580.71100.16950.069*
C90.4804 (2)0.73000 (5)−0.0131 (3)0.0539 (6)
H9A0.55800.72490.04680.065*
H9B0.49290.7264−0.13840.065*
C100.5238 (2)0.79809 (6)−0.0124 (3)0.0459 (5)
C110.6378 (2)0.79332 (6)−0.0955 (3)0.0507 (6)
H110.66300.7690−0.13110.061*
C120.4878 (2)0.83474 (6)0.0389 (3)0.0493 (6)
H120.41170.83830.09350.059*
C130.7136 (2)0.82491 (6)−0.1252 (3)0.0534 (6)
H130.78940.8214−0.18080.064*
C140.5645 (2)0.86604 (6)0.0094 (3)0.0512 (6)
H140.53930.89030.04550.061*
C150.6788 (2)0.86171 (6)−0.0736 (3)0.0487 (5)
N10.3792 (2)0.48636 (6)0.3322 (3)0.0763 (7)
N20.75855 (17)0.89324 (5)−0.0993 (3)0.0694 (6)
H2A0.82980.8898−0.14740.083*
H2B0.73610.9159−0.06690.083*
O10.29183 (19)0.47143 (5)0.4107 (3)0.1127 (8)
O20.4737 (2)0.46834 (5)0.3007 (4)0.1200 (9)
O30.32733 (13)0.63919 (4)0.1305 (2)0.0590 (4)
O40.44110 (13)0.76862 (4)0.0214 (2)0.0570 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0549 (15)0.0357 (14)0.0687 (15)0.0006 (11)−0.0019 (12)0.0067 (11)
C20.0491 (15)0.0477 (15)0.0793 (17)0.0004 (12)0.0011 (12)0.0025 (12)
C30.0561 (16)0.0499 (15)0.0664 (15)−0.0045 (12)0.0055 (12)0.0072 (12)
C40.0490 (14)0.0455 (14)0.0640 (15)−0.0046 (11)−0.0003 (11)0.0053 (11)
C50.0505 (15)0.0487 (15)0.0677 (15)0.0011 (12)0.0070 (12)0.0050 (12)
C60.0545 (14)0.0361 (13)0.0496 (13)−0.0013 (11)−0.0073 (11)0.0021 (10)
C70.0594 (15)0.0428 (14)0.0598 (14)−0.0065 (11)−0.0049 (12)0.0052 (10)
C80.0602 (15)0.0445 (14)0.0684 (15)−0.0038 (11)−0.0088 (12)0.0069 (11)
C90.0666 (16)0.0383 (13)0.0566 (14)0.0025 (11)−0.0009 (11)0.0040 (10)
C100.0493 (14)0.0380 (13)0.0504 (12)0.0008 (11)−0.0028 (10)0.0031 (10)
C110.0524 (14)0.0404 (13)0.0594 (14)0.0082 (11)0.0000 (12)−0.0023 (10)
C120.0513 (14)0.0453 (14)0.0514 (13)0.0054 (11)0.0031 (10)−0.0005 (10)
C130.0493 (14)0.0524 (15)0.0584 (14)0.0026 (11)0.0019 (11)0.0001 (11)
C140.0615 (15)0.0391 (13)0.0530 (14)0.0025 (11)−0.0022 (12)−0.0065 (10)
C150.0500 (14)0.0465 (14)0.0495 (12)−0.0027 (11)−0.0038 (11)0.0005 (10)
N10.0723 (17)0.0485 (15)0.1081 (18)0.0008 (12)0.0043 (14)0.0138 (12)
N20.0672 (13)0.0544 (13)0.0867 (15)−0.0160 (11)0.0080 (11)−0.0116 (11)
O10.0956 (16)0.0661 (13)0.176 (2)−0.0062 (11)0.0244 (15)0.0501 (13)
O20.0921 (15)0.0634 (14)0.205 (3)0.0244 (12)0.0344 (16)0.0389 (14)
O30.0557 (9)0.0410 (9)0.0805 (11)−0.0021 (7)−0.0004 (8)0.0110 (8)
O40.0583 (10)0.0381 (9)0.0745 (11)0.0006 (8)0.0061 (8)0.0040 (7)
Geometric parameters (Å, °) top
C1—C31.377 (3)C9—O41.433 (2)
C1—C21.383 (3)C9—H9A0.9700
C1—N11.453 (3)C9—H9B0.9700
C2—C41.388 (3)C10—O41.385 (2)
C2—H20.9300C10—C121.389 (3)
C3—C51.372 (3)C10—C111.393 (3)
C3—H30.9300C11—C131.390 (3)
C4—C61.390 (3)C11—H110.9300
C4—H40.9300C12—C141.387 (3)
C5—C61.394 (3)C12—H120.9300
C5—H50.9300C13—C151.391 (3)
C6—O31.361 (3)C13—H130.9300
C7—O31.440 (2)C14—C151.394 (3)
C7—C81.513 (3)C14—H140.9300
C7—H7A0.9700C15—N21.409 (3)
C7—H7B0.9700N1—O21.221 (2)
C8—C91.506 (3)N1—O11.232 (3)
C8—H8A0.9700N2—H2A0.8600
C8—H8B0.9700N2—H2B0.8600
C3—C1—C2121.3 (2)O4—C9—H9A110.1
C3—C1—N1118.6 (2)C8—C9—H9A110.1
C2—C1—N1120.1 (2)O4—C9—H9B110.1
C1—C2—C4119.5 (2)C8—C9—H9B110.1
C1—C2—H2120.2H9A—C9—H9B108.4
C4—C2—H2120.2O4—C10—C12116.53 (19)
C5—C3—C1119.3 (2)O4—C10—C11124.51 (19)
C5—C3—H3120.4C12—C10—C11119.0 (2)
C1—C3—H3120.4C13—C11—C10120.0 (2)
C2—C4—C6119.6 (2)C13—C11—H11120.0
C2—C4—H4120.2C10—C11—H11120.0
C6—C4—H4120.2C14—C12—C10120.5 (2)
C3—C5—C6120.6 (2)C14—C12—H12119.7
C3—C5—H5119.7C10—C12—H12119.7
C6—C5—H5119.7C11—C13—C15121.5 (2)
O3—C6—C4124.99 (19)C11—C13—H13119.3
O3—C6—C5115.26 (19)C15—C13—H13119.3
C4—C6—C5119.8 (2)C12—C14—C15121.17 (19)
O3—C7—C8106.95 (18)C12—C14—H14119.4
O3—C7—H7A110.3C15—C14—H14119.4
C8—C7—H7A110.3C13—C15—C14117.81 (19)
O3—C7—H7B110.3C13—C15—N2120.8 (2)
C8—C7—H7B110.3C14—C15—N2121.4 (2)
H7A—C7—H7B108.6O2—N1—O1121.3 (2)
C9—C8—C7111.73 (19)O2—N1—C1119.5 (2)
C9—C8—H8A109.3O1—N1—C1119.2 (2)
C7—C8—H8A109.3C15—N2—H2A120.0
C9—C8—H8B109.3C15—N2—H2B120.0
C7—C8—H8B109.3H2A—N2—H2B120.0
H8A—C8—H8B107.9C6—O3—C7119.42 (17)
O4—C9—C8108.19 (18)C10—O4—C9117.95 (17)
C3—C1—C2—C40.9 (3)C10—C11—C13—C150.0 (3)
N1—C1—C2—C4−179.1 (2)C10—C12—C14—C150.6 (3)
C2—C1—C3—C5−0.4 (4)C11—C13—C15—C140.0 (3)
N1—C1—C3—C5179.5 (2)C11—C13—C15—N2177.85 (19)
C1—C2—C4—C6−0.6 (3)C12—C14—C15—C13−0.3 (3)
C1—C3—C5—C6−0.3 (3)C12—C14—C15—N2−178.14 (19)
C2—C4—C6—O3179.49 (19)C3—C1—N1—O2175.7 (2)
C2—C4—C6—C5−0.1 (3)C2—C1—N1—O2−4.4 (4)
C3—C5—C6—O3−179.1 (2)C3—C1—N1—O1−4.1 (4)
C3—C5—C6—C40.6 (3)C2—C1—N1—O1175.8 (2)
O3—C7—C8—C9177.80 (17)C4—C6—O3—C7−3.4 (3)
C7—C8—C9—O4−167.07 (17)C5—C6—O3—C7176.24 (18)
O4—C10—C11—C13179.26 (19)C8—C7—O3—C6−171.25 (17)
C12—C10—C11—C130.3 (3)C12—C10—O4—C9−173.68 (17)
O4—C10—C12—C14−179.64 (18)C11—C10—O4—C97.3 (3)
C11—C10—C12—C14−0.6 (3)C8—C9—O4—C10173.62 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O1i0.862.293.123 (3)164
C3—H3···Cg1ii0.933.073.513 (4)111
C7—H7B···Cg2iii0.972.713.567 (4)148
C13—H13···Cg2iv0.933.013.757 (4)139
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1/2, y, z−3/2; (iii) x, −y−1/2, z−3/2; (iv) −x−1/2, y, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O1i0.862.293.123 (3)164
C3—H3···Cg1ii0.933.073.513 (4)111
C7—H7B···Cg2iii0.972.713.567 (4)148
C13—H13···Cg2iv0.933.013.757 (4)139
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1/2, y, z−3/2; (iii) x, −y−1/2, z−3/2; (iv) −x−1/2, y, z−1/2.
Acknowledgements top

We acknowledge the support of the National Natural Science Foundation of China (No. 20662003) and the Foundation of the Governor of Guizhou Province, China.

references
References top

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