4-Pheneth­oxy­aniline hemihydrate

Akhter, T.; Masood Siddiqi, H.; Akhter, Z.; McKee, V.

doi:10.1107/S1600536812022994

organic compounds

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Volume 68| Part 6| June 2012| Page o1912

doi:10.1107/S1600536812022994

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4-Phenethoxyaniline hemihydrate

Toheed Akhter,^a Humaira Masood Siddiqi,^a ^* Zareen Akhter ^a and Vickie McKee ^b

^aDepartment of Chemistry, Quaid-I-Azam University, Islamabad 45320, Pakistan, and ^bChemistry Department, Loughborough University, Loughborough LE11 3TU, England
^*Correspondence e-mail: humaira_siddiqi@yahoo.com

(Received 3 May 2012; accepted 19 May 2012; online 26 May 2012)

The crystal structure of the title compound, C₁₄H₁₅NO·0.5H₂O, features N—H⋯O and O—H⋯N hydrogen bonds between the amino group and water molecule of crystallization, which generate a chain along the c axis. The water molecule lies on a twofold rotation axis. A C—H⋯π interaction is observed between the phenyl and aniline rings. The angle between the mean planes of the phenyl rings is 72.51 (7)°.

Related literature

For a similar hydrogen-bonding pattern in a related structure see Haider et al. (2011 ). The title compound is a precursor of diamine monomers, which are widely used for synthesis of polyimides (PIs), see: Ragosta et al. (2011 ). For the solubility of PIs, see: Chang et al. (2010 ). Reduced solubility is associated with intermolecular hydrogen-bonding chains and stiffness, see: Hsiao & Leu (2004 ); Liaw et al. (2005 ). Incorporation of bulky pendant groups such as substituted phenyl groups into a rigid PI backbone can enhance the solubility of PIs, see: Liaw et al. (2005); Li et al. (2007 ).

Experimental

Crystal data

C₁₄H₁₅NO·0.5H₂O
M_r = 222.28
Orthorhombic, P c c 2
a = 11.6046 (8) Å
b = 13.1937 (10) Å
c = 7.9114 (6) Å
V = 1211.30 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 150 K
0.37 × 0.26 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ) T_min = 0.971, T_max = 0.991
11920 measured reflections
1633 independent reflections
1443 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.115
S = 1.09
1633 reflections
159 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1Wⁱ	0.83 (2)	2.20 (2)	3.011 (4)	166 (4)
O1W—H1W⋯N1	0.87 (2)	1.92 (2)	2.791 (4)	171 (3)
C14—H14⋯Cgⁱⁱ	0.95	2.64	3.586 (3)	173
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+2, z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812022994/kp2413sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022994/kp2413Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812022994/kp2413Isup3.cml

checkCIF report

Comment top

The title compound is a precursor of diamine monomers which are widely used for synthesis of polyimides (PIs) (Ragosta et al., 2011). Solubility of PIs is considered as one of the key property when they are used for their specific application (Chang et al., 2010). Reduced solubility is associated with intermolecular hydrogen bonding chain and stiffness (Hsiao and Leu, 2004, Liaw et al., 2005). Incorporation of bulky pendant groups such as substituted phenyl groups into rigid PI backbone can enhance the solubility of PIs (Liaw et al., 2005, Li et al., 2007). Synthesis of the title compound is aimed for introducing pendant substituted phenyl group into PI backbone and thereby improving their solubility.

Within the 1-amino-4-phenethoxybenzene molecule the two phenyl rings are tilted with respect to one another; the angle between the mean planes of the phenyl groups is 72.51 (7)° (Fig 1). The crystal structure is governed by hydrogen bonds between water molecule and the –NH₂ group (Table 1, Fig. 2) generating hydrogen bonded chains running parallel to the c axis (Fig. 2). There is also a C—H···π interaction (Fig 3).

Related literature top

For a similar hydrogen-bonding pattern in a related structure see Haider et al. (2011). The title compound is a precursor of diamine monomers which are widely used for synthesis of polyimides (PIs), see: Ragosta et al. (2011). For the solubility of PIs, see: Chang et al. (2010). Reduced solubility is associated with intermolecular hydrogen-bonding chains and stiffness, see: Hsiao & Leu (2004); Liaw et al. (2005). Incorporation of bulky pendant groups such as substituted phenyl groups into a rigid PI backbone can enhance the solubility of PIs, see: Liaw et al. (2005); Li et al. (2007).

Experimental top

A mixture of 2-phenylethanol (5 g, 40.92 mmol), anhydrous potassium carbonate (5.68 g, 40.92 mmol) and dimethyl formamide (DMF, 60 mL) was stirred for 1 h in three-necked round bottom flask under the inert atmosphere of nitrogen. Afterward solution of 1-fluoro-4-nitrobenzene in DMF was added drop wise and the reaction mixture was refluxed for 24 h at 393 K. After complete consumption of reactants, light yellow colour product was precipitated by pouring the reaction mixture into distilled water (500 mL). The crude product, after filtration and washing thoroughly with distilled water, was recrystallised from possible minimum volume of absolute ethanol. Yield was 81%.

Computing details top

Data collection: APEX2 (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The view of the asymmetric unit (O1W lies on a 2-fold axis). H-bond shown as a dashed line and thermal ellipsoids shown at 50% probability.
	Fig. 2. Packing diagram showing the H-bonded chains parallel to the c axis. H atoms omitted for clarity.
	Fig. 3. C—H ··· π interaction: C14···.Cg (C1-C6)is 3.586 (3) Å.

4-Phenethoxyaniline hemihydrate top

Crystal data top

C₁₄H₁₅NO·0.5H₂O	F(000) = 476
M_r = 222.28	D_x = 1.219 Mg m⁻³
Orthorhombic, Pcc2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 -2c	Cell parameters from 2822 reflections
a = 11.6046 (8) Å	θ = 3.1–24.1°
b = 13.1937 (10) Å	µ = 0.08 mm⁻¹
c = 7.9114 (6) Å	T = 150 K
V = 1211.30 (15) Å³	Block, colourless
Z = 4	0.37 × 0.26 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	1633 independent reflections
Radiation source: fine-focus sealed tube	1443 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω rotation with narrow frames scans	θ_max = 28.3°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −15→15
T_min = 0.971, T_max = 0.991	k = −17→17
11920 measured reflections	l = −10→10

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0593P)² + 0.2388P] where P = (F_o² + 2F_c²)/3
1633 reflections	(Δ/σ)_max < 0.001
159 parameters	Δρ_max = 0.20 e Å⁻³
6 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₄H₁₅NO·0.5H₂O	V = 1211.30 (15) Å³
M_r = 222.28	Z = 4
Orthorhombic, Pcc2	Mo Kα radiation
a = 11.6046 (8) Å	µ = 0.08 mm⁻¹
b = 13.1937 (10) Å	T = 150 K
c = 7.9114 (6) Å	0.37 × 0.26 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	1633 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	1443 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.991	R_int = 0.035
11920 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	6 restraints
wR(F²) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.20 e Å⁻³
1633 reflections	Δρ_min = −0.31 e Å⁻³
159 parameters

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.

Freidel equivalents merged since the data do not permit determination of absolute configuration.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.69069 (13)	0.95389 (11)	0.9053 (2)	0.0359 (4)
C1	0.77654 (19)	0.88571 (15)	0.8679 (3)	0.0300 (4)
C2	0.7603 (2)	0.78822 (16)	0.9316 (3)	0.0335 (5)
H2	0.6926	0.7727	0.9940	0.040*
C3	0.8422 (2)	0.71407 (16)	0.9041 (3)	0.0371 (5)
H3	0.8301	0.6478	0.9477	0.044*
C4	0.94237 (19)	0.73527 (16)	0.8132 (3)	0.0367 (5)
N1	1.0264 (2)	0.65890 (16)	0.7857 (5)	0.0583 (8)
H1B	1.091 (2)	0.680 (3)	0.766 (5)	0.087*
H1A	1.024 (3)	0.623 (3)	0.872 (4)	0.087*
C5	0.95608 (19)	0.83219 (15)	0.7463 (4)	0.0350 (5)
H5	1.0226	0.8473	0.6810	0.042*
C6	0.87417 (18)	0.90678 (15)	0.7735 (3)	0.0321 (5)
H6	0.8850	0.9726	0.7273	0.039*
C7	0.70920 (19)	1.05805 (15)	0.8599 (3)	0.0313 (5)
H7A	0.7072	1.0661	0.7355	0.038*
H7B	0.7851	1.0815	0.9016	0.038*
C8	0.61305 (18)	1.11875 (16)	0.9413 (3)	0.0340 (5)
H8A	0.5377	1.0935	0.9003	0.041*
H8B	0.6156	1.1093	1.0654	0.041*
C9	0.62423 (18)	1.23026 (15)	0.9003 (3)	0.0290 (4)
C10	0.5572 (2)	1.27416 (17)	0.7746 (3)	0.0354 (5)
H10	0.5018	1.2342	0.7165	0.042*
C11	0.5704 (2)	1.37604 (18)	0.7328 (3)	0.0421 (6)
H11	0.5251	1.4049	0.6451	0.051*
C12	0.6490 (2)	1.43509 (18)	0.8186 (4)	0.0423 (6)
H12	0.6577	1.5047	0.7905	0.051*
C13	0.71508 (19)	1.39267 (18)	0.9455 (4)	0.0408 (6)
H13	0.7687	1.4334	1.0055	0.049*
C14	0.70341 (19)	1.29072 (18)	0.9856 (3)	0.0346 (5)
H14	0.7499	1.2620	1.0720	0.042*
O1W	1.0000	0.5000	0.5561 (6)	0.0725 (10)
H1W	1.005 (5)	0.5538 (8)	0.620 (4)	0.109*
X1A	0.8586	0.8104	0.8394	0.040*	0.00

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0365 (8)	0.0254 (7)	0.0457 (10)	−0.0005 (6)	0.0102 (8)	0.0010 (7)
C1	0.0334 (10)	0.0252 (9)	0.0313 (10)	−0.0025 (8)	0.0001 (9)	−0.0028 (8)
C2	0.0362 (11)	0.0304 (11)	0.0338 (12)	−0.0068 (8)	0.0013 (10)	0.0018 (9)
C3	0.0451 (12)	0.0250 (10)	0.0411 (12)	−0.0050 (9)	−0.0031 (11)	0.0062 (9)
C4	0.0345 (11)	0.0266 (10)	0.0490 (14)	0.0016 (8)	−0.0050 (11)	−0.0002 (10)
N1	0.0451 (13)	0.0311 (10)	0.099 (2)	0.0077 (9)	0.0094 (15)	0.0114 (13)
C5	0.0325 (10)	0.0277 (10)	0.0448 (13)	−0.0040 (8)	0.0026 (10)	−0.0010 (10)
C6	0.0359 (11)	0.0228 (9)	0.0377 (11)	−0.0032 (8)	0.0038 (10)	−0.0001 (9)
C7	0.0354 (10)	0.0251 (9)	0.0334 (11)	0.0000 (8)	0.0044 (9)	0.0000 (8)
C8	0.0325 (10)	0.0294 (10)	0.0400 (13)	0.0011 (8)	0.0055 (10)	−0.0002 (9)
C9	0.0282 (9)	0.0291 (9)	0.0296 (10)	0.0041 (8)	0.0058 (8)	−0.0020 (9)
C10	0.0358 (11)	0.0363 (11)	0.0340 (12)	0.0072 (9)	−0.0064 (10)	−0.0084 (9)
C11	0.0477 (14)	0.0405 (12)	0.0382 (13)	0.0155 (11)	−0.0042 (11)	0.0002 (11)
C12	0.0456 (13)	0.0281 (10)	0.0532 (16)	0.0072 (9)	0.0074 (12)	0.0018 (11)
C13	0.0329 (11)	0.0350 (11)	0.0546 (16)	−0.0039 (9)	−0.0013 (11)	−0.0069 (11)
C14	0.0298 (10)	0.0376 (11)	0.0364 (12)	0.0005 (9)	−0.0043 (9)	0.0003 (10)
O1W	0.083 (2)	0.0438 (14)	0.090 (3)	−0.004 (2)	0.000	0.000

Geometric parameters (Å, º) top

O1—C1	1.374 (3)	C8—C9	1.512 (3)
O1—C7	1.437 (2)	C8—H8A	0.9900
C1—C6	1.385 (3)	C8—H8B	0.9900
C1—C2	1.394 (3)	C9—C10	1.389 (3)
C2—C3	1.381 (3)	C9—C14	1.391 (3)
C2—H2	0.9500	C10—C11	1.393 (3)
C3—C4	1.396 (3)	C10—H10	0.9500
C3—H3	0.9500	C11—C12	1.378 (4)
C4—C5	1.393 (3)	C11—H11	0.9500
C4—N1	1.419 (3)	C12—C13	1.382 (4)
N1—H1B	0.818 (18)	C12—H12	0.9500
N1—H1A	0.834 (18)	C13—C14	1.389 (3)
C5—C6	1.385 (3)	C13—H13	0.9500
C5—H5	0.9500	C14—H14	0.9500
C6—H6	0.9500	O1W—H1W	0.873 (19)
C7—C8	1.517 (3)	X1A—H14ⁱ	2.6415
C7—H7A	0.9900	X1A—C14ⁱ	3.586 (2)
C7—H7B	0.9900

C1—O1—C7	117.64 (17)	H7A—C7—H7B	108.6
O1—C1—C6	125.28 (18)	C9—C8—C7	111.07 (17)
O1—C1—C2	115.34 (19)	C9—C8—H8A	109.4
C6—C1—C2	119.4 (2)	C7—C8—H8A	109.4
C3—C2—C1	120.2 (2)	C9—C8—H8B	109.4
C3—C2—H2	119.9	C7—C8—H8B	109.4
C1—C2—H2	119.9	H8A—C8—H8B	108.0
C2—C3—C4	120.8 (2)	C10—C9—C14	118.5 (2)
C2—C3—H3	119.6	C10—C9—C8	120.7 (2)
C4—C3—H3	119.6	C14—C9—C8	120.7 (2)
C5—C4—C3	118.4 (2)	C9—C10—C11	120.8 (2)
C5—C4—N1	121.0 (2)	C9—C10—H10	119.6
C3—C4—N1	120.6 (2)	C11—C10—H10	119.6
C4—N1—H1B	115 (3)	C12—C11—C10	120.1 (2)
C4—N1—H1A	104 (3)	C12—C11—H11	120.0
H1B—N1—H1A	112 (3)	C10—C11—H11	120.0
C6—C5—C4	121.0 (2)	C11—C12—C13	119.7 (2)
C6—C5—H5	119.5	C11—C12—H12	120.1
C4—C5—H5	119.5	C13—C12—H12	120.1
C1—C6—C5	120.2 (2)	C12—C13—C14	120.3 (2)
C1—C6—H6	119.9	C12—C13—H13	119.9
C5—C6—H6	119.9	C14—C13—H13	119.9
O1—C7—C8	106.79 (17)	C13—C14—C9	120.6 (2)
O1—C7—H7A	110.4	C13—C14—H14	119.7
C8—C7—H7A	110.4	C9—C14—H14	119.7
O1—C7—H7B	110.4	H14ⁱ—X1A—C14ⁱ	1.9
C8—C7—H7B	110.4

Symmetry code: (i) x, −y+2, z−1/2.

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1Wⁱⁱ	0.83 (2)	2.20 (2)	3.011 (4)	166 (4)
O1W—H1W···N1	0.87 (2)	1.92 (2)	2.791 (4)	171 (3)
C14—H14···Cgⁱⁱⁱ	0.95	2.64	3.586 (3)	173

Symmetry codes: (ii) x, −y+1, z+1/2; (iii) x, −y+2, z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₅NO·0.5H₂O
M_r	222.28
Crystal system, space group	Orthorhombic, Pcc2
Temperature (K)	150
a, b, c (Å)	11.6046 (8), 13.1937 (10), 7.9114 (6)
V (Å³)	1211.30 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.37 × 0.26 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008)
T_min, T_max	0.971, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	11920, 1633, 1443
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.115, 1.09
No. of reflections	1633
No. of parameters	159
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.31

Computer programs: APEX2 (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1Wⁱ	0.834 (18)	2.196 (19)	3.011 (4)	166 (4)
O1W—H1W···N1	0.873 (19)	1.92 (2)	2.791 (4)	171 (3)
C14—H14···Cgⁱⁱ	0.95	2.64	3.586 (3)	172.7

Symmetry codes: (i) x, −y+1, z+1/2; (ii) x, −y+2, z+3/2.

Acknowledgements

The authors are grateful to the Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan, for providing laboratory facilities to carry out this work.

References

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