organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890
Volume 65| Part 5| May 2009| Page o1096

4,4′-(Hexane-1,6-diyldi­­oxy)dianiline

aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and bInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
*Correspondence e-mail: zareenakhter@yahoo.com

(Received 4 April 2009; accepted 7 April 2009; online 22 April 2009)

The complete molecule of the title compound, C18H24N2O2, is generated by a crystallographic inversion centre. The torsion angles in the hexa­methyl­ene chain are consistent with an anti­periplanar conformation, whereas the conformation of the O—CH2—CH2—CH2 unit is gauche. The three-dimensional crystal packing is stabilized by N—H⋯O and N—H⋯N hydrogen bonding.

Related literature

For aromatic diamines as building blocks for the preparation of high-performance polymers, see: Mehdipour-Ataei (2005[Mehdipour-Ataei, S. (2005). Eur. Polym. J. 41, 65-71.]; Mehdipour-Ataei et al. (2007[Mehdipour-Ataei, S., Tadjarodi, A. & Babanzadeh, S. (2007). Eur. Polym. J. 43, 498-506.]). For the use of flexible linkages, see: Shao et al. (2007[Shao, Y., Li, Y., Zhao, X., Ma, T., Gong, C. & Yang, F. (2007). Eur. Polym. J. 43, 4389-4397.]); Yin et al. (1998[Yin, J., Ye, Y. F. & Wang, Z. G. (1998). Eur. Polym. J. 34, 1839-1843.]).

[Scheme 1]

Experimental

Crystal data
  • C18H24N2O2

  • Mr = 300.39

  • Orthorhombic, P b c a

  • a = 5.4777 (6) Å

  • b = 13.6049 (12) Å

  • c = 21.7278 (18) Å

  • V = 1619.2 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 173 K

  • 0.33 × 0.23 × 0.11 mm

Data collection
  • Stoe IPDS-II two-circle diffractometer

  • Absorption correction: none

  • 9301 measured reflections

  • 1854 independent reflections

  • 1403 reflections with I > 2σ(I)

  • Rint = 0.056

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.103

  • S = 1.02

  • 1854 reflections

  • 109 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯N1i 0.939 (18) 2.318 (18) 3.2248 (11) 162.1 (13)
N1—H1B⋯O1ii 0.899 (16) 2.318 (16) 3.1724 (14) 158.6 (13)
Symmetry codes: (i) [x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]; (ii) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z].

Data collection: X-AREA (Stoe & Cie, 2001[Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and XP (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Aromatic diamines are valuable building blocks for the preparation of high-performance polymers including polyamides, polyimides and polyureas (Mehdipour-Ataei, 2005). Therefore, these can be used to produce desired alterations in the chemical nature of macromolecular chains (Mehdipour-Ataei et al., 2007). Much research in recent years has focused on the design and synthesis of novel diamines in order to obtain suitable polymers. One of the popular approaches to achieve this goal is the introduction of flexible linkages such as an ether moiety (Shao et al., 2007) and/or methylene spacers (Yin et al., 1998) in the core structure of the diamines. These linkages increase the degree of freedom by reducing the segmental rotational barrier and inhibit close chain packing. The title compound, (I), in which flexible methylene spacers are present between the aryl ether moieties, is an outcome of efforts to modify the aromatic diamine monomers by flexible linkages in order to improve the processability and performance of the resulting polymers.

Molecules of (I) (Fig. 1) are located about a crystallographic centre of inversion. All torsion angles in the hexamethylene chain indicate an antiperiplanar conformation whereas the conformation of the O—CH2—CH2—CH2 unit is gauche. The crystal packing (Table 1) is stabilized by N—H···O and N—H···N hydrogen bonds which lead to a three-dimensional network.

Related literature top

For aromatic diamines as building blocks for the preparation of

high-performance polymers, see: Mehdipour-Ataei (2005; Mehdipour-Ataei et al. (2007). For the use of flexible linkages, see: Shao et al. (2007); Yin et al. (1998).

Experimental top

The title compound (I) was synthesized in two steps. In the first step, bis(4-nitrophenoxy)hexane was prepared by Williamson's reaction. A three-neck round bottom flask equipped with Dean-Stark trap, thermometer, magnetic stirrer and nitrogen inlet was charged with a suspension of 1,6-hexane diol (2.25 g; 19.1 mmol) and anhydrous potassium carbonate (5.3 g; 38.2 mmol) in a mixture of N,N'-dimethyl formamide (DMF) (60 ml) and toluene (20 ml), and refluxed (at 403–408 K) for 2 h for azeotropic removal of water. After cooling to 343–343 K, 1-fluoro-4-nitro benzene (4.05 ml; 38.2 mmol) was added and the mixture was again refluxed for 6 h. Subsequently, some toluene was distilled off and the resulting mixture was poured into 500 ml of chilled water after cooling to room temperature. The crude product was filtered as yellow solid, washed thoroughly with water and recrystallized from ethanol to afford bis(4-nitrophenoxy)hexane. In the second step, a two-neck flask was charged with 1,6-bis(4-nitrophenoxy)hexane (2.5 g; 6.94 mmol), hydrazine monohydrate (10 ml), ethanol (80 ml) and 0.1 g of 5% palladium on carbon (Pd–C). The mixture was refluxed for 18 h and then filtered to remove the Pd–C. The filtrate was concentrated on rotary evaporator to remove the solvent and the resulting crude solid was recrystallized from ethanol to afford colourless crystals suitable for X-ray analysis, which were stored in air-tight glass bottles for further studies. Yield 72%; m.p. 414 K. Elemental analysis. Found C, 72.03, H, 7.90, N, 9.25. Calculated for C18H24N2O2: C, 71.97, H, 8.05, N, 9.33; IR (KBr pellet) in cm-1: 3395, 3311 (NH2), 1632 (N-H bending), 1385 (C-N stretching), 1233 (C-O-C), 2935 (C—H aliphatic), 3219 (C—H aromatic). 1H NMR (CDCl3) δ: 3.92 (s, 4H, NH2), 6.40 (d, 4H, J = 3.0 Hz), 6.70 (d, 4H, J = 2.9 Hz), 3.88 (t, 4H), 1.78 (m, 4H), 1.51 (m, 4H) p.p.m. 13C NMR (CDCl3) δ: 147.52 (2 C, C4), 139.83 (2 C, C1), 116.42 (4 C, C2,2'), 115.67 (4 C, C3,3'), 68.54 (2 C, C5), 29.38 (2 C, C6), 25.91 (2 C, C7) p.p.m.

Refinement top

H atoms bonded to C were geometrically positioned and refined using a riding model with with C—H(aromatic) = 0.95Å and CH(methylene) = 0.99 Å, and with U(H) = 1.2 Ueq(C). The H atoms bonded to N were freely refined, see Table 1 for distances.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and XP (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Perspective view of (I) showing the atom labelling scheme and displacement ellipsoids at the 50% probability level. H atoms are drawn as spheres of arbitrary radii. Unlabelled atoms are related by the symmetry operator 1 - x, -y, 1 - z.
4,4'-(Hexane-1,6-diyldioxy)dianiline top
Crystal data top
C18H24N2O2F(000) = 648
Mr = 300.39Dx = 1.232 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 6791 reflections
a = 5.4777 (6) Åθ = 3.6–27.7°
b = 13.6049 (12) ŵ = 0.08 mm1
c = 21.7278 (18) ÅT = 173 K
V = 1619.2 (3) Å3Plate, colourless
Z = 40.33 × 0.23 × 0.11 mm
Data collection top
Stoe IPDS-II two-circle
diffractometer
1403 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.056
Graphite monochromatorθmax = 27.6°, θmin = 3.5°
ω scansh = 75
9301 measured reflectionsk = 1717
1854 independent reflectionsl = 2428
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)] = 0.039H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103 w = 1/[σ2(Fo2) + (0.0626P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
1854 reflectionsΔρmax = 0.24 e Å3
109 parametersΔρmin = 0.18 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.016 (2)
Crystal data top
C18H24N2O2V = 1619.2 (3) Å3
Mr = 300.39Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 5.4777 (6) ŵ = 0.08 mm1
b = 13.6049 (12) ÅT = 173 K
c = 21.7278 (18) Å0.33 × 0.23 × 0.11 mm
Data collection top
Stoe IPDS-II two-circle
diffractometer
1403 reflections with I > 2σ(I)
9301 measured reflectionsRint = 0.056
1854 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 1.02Δρmax = 0.24 e Å3
1854 reflectionsΔρmin = 0.18 e Å3
109 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.9705 (2)0.55262 (7)0.71082 (5)0.0289 (3)
H1A1.131 (3)0.5464 (11)0.7257 (7)0.045 (4)*
H1B0.956 (3)0.6080 (11)0.6885 (7)0.044 (4)*
O10.60683 (17)0.20721 (5)0.60327 (4)0.0303 (2)
C10.8839 (2)0.46681 (8)0.68123 (5)0.0235 (3)
C20.6800 (2)0.47129 (8)0.64298 (5)0.0258 (3)
H20.60600.53320.63510.031*
C30.5818 (2)0.38691 (8)0.61598 (5)0.0255 (3)
H30.44320.39170.58990.031*
C40.6879 (2)0.29578 (8)0.62748 (5)0.0237 (3)
C50.8897 (2)0.29005 (8)0.66663 (5)0.0262 (3)
H50.96040.22790.67550.031*
C60.9879 (2)0.37456 (8)0.69278 (5)0.0259 (3)
H61.12700.36970.71870.031*
C70.3984 (2)0.20972 (8)0.56312 (5)0.0269 (3)
H7A0.43630.24780.52550.032*
H7B0.25820.24100.58410.032*
C80.3376 (2)0.10382 (8)0.54656 (5)0.0267 (3)
H8A0.17700.10240.52570.032*
H8B0.32270.06520.58500.032*
C90.5262 (2)0.05471 (7)0.50505 (5)0.0248 (3)
H9A0.69000.06210.52370.030*
H9B0.52820.08850.46470.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0355 (7)0.0239 (5)0.0274 (5)0.0043 (4)0.0043 (5)0.0005 (4)
O10.0369 (6)0.0204 (4)0.0336 (5)0.0005 (3)0.0102 (4)0.0031 (3)
C10.0284 (6)0.0230 (5)0.0192 (5)0.0030 (4)0.0032 (5)0.0002 (4)
C20.0311 (7)0.0213 (5)0.0251 (6)0.0025 (5)0.0006 (5)0.0002 (4)
C30.0271 (6)0.0256 (6)0.0238 (5)0.0003 (4)0.0023 (5)0.0001 (4)
C40.0277 (7)0.0209 (5)0.0226 (5)0.0018 (4)0.0012 (5)0.0021 (4)
C50.0295 (7)0.0222 (5)0.0269 (6)0.0036 (4)0.0000 (5)0.0001 (4)
C60.0249 (6)0.0287 (6)0.0241 (5)0.0004 (5)0.0025 (5)0.0000 (4)
C70.0283 (7)0.0248 (6)0.0275 (6)0.0012 (5)0.0018 (5)0.0031 (4)
C80.0277 (7)0.0253 (6)0.0271 (6)0.0030 (4)0.0004 (5)0.0025 (4)
C90.0259 (6)0.0234 (6)0.0250 (5)0.0041 (4)0.0005 (5)0.0015 (4)
Geometric parameters (Å, º) top
N1—C11.4147 (14)C5—C61.3908 (16)
N1—H1A0.939 (18)C5—H50.9500
N1—H1B0.899 (16)C6—H60.9500
O1—C41.3879 (13)C7—C81.5218 (15)
O1—C71.4372 (15)C7—H7A0.9900
C1—C21.3937 (17)C7—H7B0.9900
C1—C61.4011 (15)C8—C91.5258 (16)
C2—C31.3968 (15)C8—H8A0.9900
C2—H20.9500C8—H8B0.9900
C3—C41.3919 (16)C9—C9i1.532 (2)
C3—H30.9500C9—H9A0.9900
C4—C51.3966 (17)C9—H9B0.9900
C1—N1—H1A113.3 (10)C5—C6—H6119.7
C1—N1—H1B114.7 (10)C1—C6—H6119.7
H1A—N1—H1B110.0 (14)O1—C7—C8107.15 (9)
C4—O1—C7117.63 (8)O1—C7—H7A110.3
C2—C1—C6118.16 (10)C8—C7—H7A110.3
C2—C1—N1120.25 (10)O1—C7—H7B110.3
C6—C1—N1121.43 (11)C8—C7—H7B110.3
C1—C2—C3121.54 (10)H7A—C7—H7B108.5
C1—C2—H2119.2C7—C8—C9113.96 (10)
C3—C2—H2119.2C7—C8—H8A108.8
C4—C3—C2119.72 (11)C9—C8—H8A108.8
C4—C3—H3120.1C7—C8—H8B108.8
C2—C3—H3120.1C9—C8—H8B108.8
O1—C4—C3124.86 (11)H8A—C8—H8B107.7
O1—C4—C5115.83 (9)C8—C9—C9i112.53 (12)
C3—C4—C5119.31 (10)C8—C9—H9A109.1
C6—C5—C4120.58 (10)C9i—C9—H9A109.1
C6—C5—H5119.7C8—C9—H9B109.1
C4—C5—H5119.7C9i—C9—H9B109.1
C5—C6—C1120.67 (11)H9A—C9—H9B107.8
C6—C1—C2—C30.75 (17)C3—C4—C5—C61.58 (18)
N1—C1—C2—C3176.24 (11)C4—C5—C6—C11.14 (18)
C1—C2—C3—C40.31 (18)C2—C1—C6—C50.03 (17)
C7—O1—C4—C30.28 (17)N1—C1—C6—C5175.46 (10)
C7—O1—C4—C5179.52 (10)C4—O1—C7—C8176.37 (9)
C2—C3—C4—O1179.93 (11)O1—C7—C8—C969.25 (12)
C2—C3—C4—C50.85 (17)C7—C8—C9—C9i173.85 (12)
O1—C4—C5—C6179.13 (10)
Symmetry code: (i) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N1ii0.939 (18)2.318 (18)3.2248 (11)162.1 (13)
N1—H1B···O1iii0.899 (16)2.318 (16)3.1724 (14)158.6 (13)
Symmetry codes: (ii) x+1/2, y, z+3/2; (iii) x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC18H24N2O2
Mr300.39
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)173
a, b, c (Å)5.4777 (6), 13.6049 (12), 21.7278 (18)
V3)1619.2 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.33 × 0.23 × 0.11
Data collection
DiffractometerStoe IPDS-II two-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
9301, 1854, 1403
Rint0.056
(sin θ/λ)max1)0.652
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.103, 1.02
No. of reflections1854
No. of parameters109
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.24, 0.18

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and XP (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N1i0.939 (18)2.318 (18)3.2248 (11)162.1 (13)
N1—H1B···O1ii0.899 (16)2.318 (16)3.1724 (14)158.6 (13)
Symmetry codes: (i) x+1/2, y, z+3/2; (ii) x+3/2, y+1/2, z.
 

Acknowledgements

The authors are grateful to the Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan, and the Institute for Inorganic Chemistry, University of Frankfurt, Germany, for providing laboratory and analytical facilities.

References

First citationMehdipour-Ataei, S. (2005). Eur. Polym. J. 41, 65–71.  Web of Science CrossRef CAS Google Scholar
First citationMehdipour-Ataei, S., Tadjarodi, A. & Babanzadeh, S. (2007). Eur. Polym. J. 43, 498–506.  Web of Science CrossRef CAS Google Scholar
First citationShao, Y., Li, Y., Zhao, X., Ma, T., Gong, C. & Yang, F. (2007). Eur. Polym. J. 43, 4389–4397.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationStoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.  Google Scholar
First citationYin, J., Ye, Y. F. & Wang, Z. G. (1998). Eur. Polym. J. 34, 1839–1843.  Web of Science CrossRef CAS Google Scholar

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 65| Part 5| May 2009| Page o1096
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