6-(4-Nitro­phen­oxy)hexa­nol

Saif Ullah Khan, M.; Akhter, Z.; Bolte, M.; Cheema, S.A.; Siddiqi, H.M.

doi:10.1107/S160053680901722X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1285

doi:10.1107/S160053680901722X

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6-(4-Nitrophenoxy)hexanol

Muhammad Saif Ullah Khan,^a Zareen Akhter,^a ^* Michael Bolte,^b Sajjad A. Cheema ^c and Humaira M. Siddiqi ^a

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main, Germany, and ^cAlchemist SAC, PO Box 321, Faisalabad 38000, Pakistan
^*Correspondence e-mail: zareenakhter@yahoo.com

(Received 4 May 2009; accepted 7 May 2009; online 14 May 2009)

The title compound, C₁₂H₁₇NO₄, features an almost planar molecule (r.m.s. deviation for all non-H atoms = 0.070 Å). All methylene C—C bonds adopt an antiperiplanar conformation. In the crystal structure the molecules lie in planes parallel to (1 $[\overline{1}]$ 2) and the packing is stabilized by O—H⋯O hydrogen bonds.

Related literature

For background material on polymers and their properties, see: Manners (1999 ); Jarzabek et al. (1999 ) Schab-Balcerzak et al. (2002 ); Choi et al. (2004 ); Hsiao & Lin (2004 ); Shao et al. (2007 ); Shockravi et al. (2007 ); Yin et al. (1998 ). For studies on a related compound, see: Saeed et al. (2008 ).

Experimental

Crystal data

C₁₂H₁₇NO₄
M_r = 239.27
Triclinic, $[P \overline 1]$
a = 5.4410 (7) Å
b = 10.2270 (11) Å
c = 11.3333 (14) Å
α = 96.993 (9)°
β = 103.818 (10)°
γ = 99.516 (10)°
V = 595.34 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 173 K
0.25 × 0.24 × 0.12 mm

Data collection

STOE IPDS II diffractometer
Absorption correction: none
5002 measured reflections
2105 independent reflections
1694 reflections with I > 2σ(I)
R_int = 0.074

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.185
S = 1.04
2105 reflections
159 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4ⁱ	0.83 (5)	2.10 (5)	2.905 (2)	163 (4)
Symmetry code: (i) x-1, y+1, z+1.

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

Supporting information

Crystal structure: contains datablock I. DOI: 10.1107/S160053680901722X/tk2444sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680901722X/tk2444Isup2.hkl

checkCIF report

Comment top

Polymers are ubiquitous because of their tremendous processing advantage over ceramics and metals (Manners, 1999). Therefore, much research in recent years has focused upon producing speciality polymers with a better balance of properties (Shockravi et al., 2007). The goal can be achieved by inducing desired modifications in the polymer core structure (Saeed et al., 2008). Flexible linkages such as for the aryl-ether moiety (Shao et al., 2007) and/or methylene spacers (Yin et al., 1998) can be introduced into the macro chain in order to obtain desirable polymers. It has been recognized that the incorporation of an aryl-ether moiety generally imparts enhanced solubility and processability while maintaining the toughness of the polymers (Hsiao & Lin, 2004). Moreover, the addition of aliphatic methylene spacers between the aromatic moieties increases the degree of freedom by reducing the segmental barrier and effectively disrupts potential intermolecular interactions (Schab-Balcerzak et al., 2002). Furthermore, the inclusion of these flexible linkages in the polymer core structure also imparts mesogenic (Choi et al., 2004) and optical properties (Jarzabek et al., 1999) to the resulting polymer. Thus, the final polymer produced by the introduction of these linkages exhibits not an enhancement in its processability but also an improvement in its performance (Jarzabek et al., 1999). The title compound, (I), Fig. 1, is a flexible nitro-alcohol precursor with built-in aliphatic (methylene) groups along with aryl-ether moiety, which was prepared as part of our quest to design and synthesize structurally modified monomers for processable high performance polymers (Saeed et al., 2008).

Related literature top

For background material on polymers and their properties, see: Manners (1999); Jarzabek et al. (1999) Schab-Balcerzak et al. (2002); Choi et al. (2004); Hsiao & Lin (2004); Shao et al. (2007); Shockravi et al. (2007); (Yin et al., 1998). For studies on a related polymer, see: Saeed et al. (2008).

Experimental top

The title compound (I) was synthesized by Williamson's etherification of 1,6-hexane diol and p-nitrochlorobenzene. A three-necked round bottom flask equipped with reflux condenser, thermometer and nitrogen inlet was charged with a suspension of 1,6-hexane diol (2.5 g; 21 mmol) and anhydrous potassium carbonate (2.93 g; 21 mmol) in dimethylformamide (60 ml) and stirred for 30 mins. Then p-nitrochlorobenzene (3.33 g; 21 mmol) was added dropwise to the suspension and the resulting mixture was heated to 383 K for 6 h. The reaction mixture was poured into 500 ml of chilled water, cooled to room temperature and the crude product was filtered as a light-yellow solid mass. The product was then washed thoroughly with water, dissolved in ethanol and set aside for crystallization. Yield 74%, m.p. 357 K.

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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Perspective view of (I) with the atom numbering scheme. Displacement ellipsoids are at the 50% probability level and H atoms are drawn as small spheres of arbitrary radii.

6-(4-Nitrophenoxy)hexanol top

Crystal data top

C₁₂H₁₇NO₄	Z = 2
M_r = 239.27	F(000) = 256
Triclinic, P1	D_x = 1.335 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.4410 (7) Å	Cell parameters from 4859 reflections
b = 10.2270 (11) Å	θ = 3.8–25.6°
c = 11.3333 (14) Å	µ = 0.10 mm⁻¹
α = 96.993 (9)°	T = 173 K
β = 103.818 (10)°	Plate, yellow
γ = 99.516 (10)°	0.25 × 0.24 × 0.12 mm
V = 595.34 (12) Å³

Data collection top

STOE IPDS II two-circle- diffractometer	1694 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.074
Graphite monochromator	θ_max = 25.0°, θ_min = 3.8°
ω scans	h = −6→6
5002 measured reflections	k = −12→12
2105 independent reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.066	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.185	w = 1/[σ²(F_o²) + (0.1186P)² + 0.0716P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2105 reflections	Δρ_max = 0.31 e Å⁻³
159 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.029 (8)

Crystal data top

C₁₂H₁₇NO₄	γ = 99.516 (10)°
M_r = 239.27	V = 595.34 (12) Å³
Triclinic, P1	Z = 2
a = 5.4410 (7) Å	Mo Kα radiation
b = 10.2270 (11) Å	µ = 0.10 mm⁻¹
c = 11.3333 (14) Å	T = 173 K
α = 96.993 (9)°	0.25 × 0.24 × 0.12 mm
β = 103.818 (10)°

Data collection top

STOE IPDS II two-circle- diffractometer	1694 reflections with I > 2σ(I)
5002 measured reflections	R_int = 0.074
2105 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.185	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.31 e Å⁻³
2105 reflections	Δρ_min = −0.33 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.

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

	x	y	z	U_iso*/U_eq
N1	0.7262 (3)	0.23792 (17)	−0.02359 (16)	0.0296 (4)
O1	0.1593 (3)	1.17994 (15)	0.78559 (16)	0.0418 (5)
H1	0.058 (9)	1.200 (5)	0.826 (4)	0.107 (15)*
O2	0.2906 (3)	0.47709 (14)	0.32079 (13)	0.0310 (4)
O3	0.6941 (3)	0.11523 (15)	−0.04278 (16)	0.0428 (5)
O4	0.8558 (3)	0.30971 (15)	−0.07523 (14)	0.0385 (5)
C1	0.0903 (4)	1.0372 (2)	0.7533 (2)	0.0321 (5)
H1A	−0.0980	1.0087	0.7153	0.039*
H1B	0.1349	0.9954	0.8278	0.039*
C2	0.2376 (4)	0.9931 (2)	0.6628 (2)	0.0313 (5)
H2A	0.4248	1.0151	0.7046	0.038*
H2B	0.2081	1.0444	0.5938	0.038*
C3	0.1586 (4)	0.8432 (2)	0.6108 (2)	0.0297 (5)
H3A	0.1895	0.7916	0.6795	0.036*
H3B	−0.0287	0.8209	0.5693	0.036*
C4	0.3067 (4)	0.8006 (2)	0.51947 (19)	0.0304 (5)
H4A	0.2806	0.8547	0.4525	0.036*
H4B	0.4935	0.8207	0.5620	0.036*
C5	0.2263 (4)	0.6526 (2)	0.46311 (19)	0.0307 (5)
H5A	0.2555	0.5975	0.5292	0.037*
H5B	0.0395	0.6314	0.4205	0.037*
C6	0.3777 (4)	0.6177 (2)	0.37264 (19)	0.0310 (5)
H6A	0.3505	0.6729	0.3064	0.037*
H6B	0.5645	0.6365	0.4150	0.037*
C11	0.4034 (4)	0.4260 (2)	0.23531 (18)	0.0259 (5)
C12	0.5917 (4)	0.5012 (2)	0.19465 (19)	0.0292 (5)
H12	0.6492	0.5948	0.2255	0.035*
C13	0.6963 (4)	0.4383 (2)	0.10791 (19)	0.0289 (5)
H13	0.8253	0.4886	0.0785	0.035*
C14	0.6111 (4)	0.3028 (2)	0.06527 (18)	0.0260 (5)
C15	0.4211 (4)	0.2257 (2)	0.10414 (19)	0.0305 (5)
H15	0.3649	0.1321	0.0734	0.037*
C16	0.3156 (4)	0.2890 (2)	0.18899 (19)	0.0295 (5)
H16	0.1824	0.2389	0.2160	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0340 (9)	0.0249 (9)	0.0317 (9)	0.0102 (7)	0.0134 (8)	−0.0030 (7)
O1	0.0510 (10)	0.0244 (8)	0.0567 (11)	0.0068 (7)	0.0347 (9)	−0.0067 (7)
O2	0.0334 (8)	0.0262 (8)	0.0349 (8)	0.0050 (6)	0.0182 (7)	−0.0067 (6)
O3	0.0568 (11)	0.0237 (9)	0.0532 (10)	0.0128 (7)	0.0276 (8)	−0.0055 (7)
O4	0.0477 (10)	0.0330 (9)	0.0428 (9)	0.0097 (7)	0.0290 (8)	0.0012 (6)
C1	0.0358 (11)	0.0231 (11)	0.0404 (12)	0.0063 (8)	0.0196 (9)	−0.0037 (8)
C2	0.0319 (11)	0.0290 (12)	0.0348 (11)	0.0060 (9)	0.0171 (9)	−0.0043 (9)
C3	0.0291 (10)	0.0280 (11)	0.0339 (11)	0.0088 (8)	0.0142 (9)	−0.0041 (8)
C4	0.0298 (10)	0.0289 (11)	0.0340 (11)	0.0071 (9)	0.0153 (9)	−0.0037 (8)
C5	0.0314 (11)	0.0314 (12)	0.0315 (11)	0.0092 (9)	0.0149 (9)	−0.0029 (8)
C6	0.0366 (11)	0.0260 (11)	0.0322 (11)	0.0080 (9)	0.0168 (9)	−0.0057 (8)
C11	0.0271 (10)	0.0270 (11)	0.0256 (10)	0.0098 (8)	0.0109 (8)	−0.0022 (8)
C12	0.0338 (11)	0.0227 (10)	0.0317 (11)	0.0054 (8)	0.0141 (8)	−0.0040 (8)
C13	0.0327 (10)	0.0247 (10)	0.0316 (11)	0.0061 (8)	0.0155 (9)	−0.0013 (8)
C14	0.0292 (10)	0.0246 (11)	0.0258 (10)	0.0098 (8)	0.0108 (8)	−0.0030 (8)
C15	0.0361 (11)	0.0208 (10)	0.0346 (11)	0.0066 (8)	0.0128 (9)	−0.0039 (8)
C16	0.0316 (10)	0.0242 (11)	0.0343 (11)	0.0038 (8)	0.0160 (9)	−0.0011 (8)

Geometric parameters (Å, º) top

N1—O3	1.223 (2)	C4—H4A	0.9900
N1—O4	1.228 (2)	C4—H4B	0.9900
N1—C14	1.457 (2)	C5—C6	1.506 (3)
O1—C1	1.425 (2)	C5—H5A	0.9900
O1—H1	0.83 (5)	C5—H5B	0.9900
O2—C11	1.362 (2)	C6—H6A	0.9900
O2—C6	1.441 (2)	C6—H6B	0.9900
C1—C2	1.516 (3)	C11—C12	1.381 (3)
C1—H1A	0.9900	C11—C16	1.395 (3)
C1—H1B	0.9900	C12—C13	1.392 (3)
C2—C3	1.525 (3)	C12—H12	0.9500
C2—H2A	0.9900	C13—C14	1.373 (3)
C2—H2B	0.9900	C13—H13	0.9500
C3—C4	1.522 (3)	C14—C15	1.385 (3)
C3—H3A	0.9900	C15—C16	1.381 (3)
C3—H3B	0.9900	C15—H15	0.9500
C4—C5	1.517 (3)	C16—H16	0.9500

O3—N1—O4	122.51 (16)	C6—C5—H5A	109.5
O3—N1—C14	119.32 (17)	C4—C5—H5A	109.5
O4—N1—C14	118.16 (16)	C6—C5—H5B	109.5
C1—O1—H1	105 (3)	C4—C5—H5B	109.5
C11—O2—C6	117.46 (15)	H5A—C5—H5B	108.0
O1—C1—C2	108.19 (17)	O2—C6—C5	108.46 (17)
O1—C1—H1A	110.1	O2—C6—H6A	110.0
C2—C1—H1A	110.1	C5—C6—H6A	110.0
O1—C1—H1B	110.1	O2—C6—H6B	110.0
C2—C1—H1B	110.1	C5—C6—H6B	110.0
H1A—C1—H1B	108.4	H6A—C6—H6B	108.4
C1—C2—C3	113.07 (17)	O2—C11—C12	123.92 (18)
C1—C2—H2A	109.0	O2—C11—C16	115.44 (17)
C3—C2—H2A	109.0	C12—C11—C16	120.64 (17)
C1—C2—H2B	109.0	C11—C12—C13	119.14 (19)
C3—C2—H2B	109.0	C11—C12—H12	120.4
H2A—C2—H2B	107.8	C13—C12—H12	120.4
C4—C3—C2	112.49 (18)	C14—C13—C12	119.37 (19)
C4—C3—H3A	109.1	C14—C13—H13	120.3
C2—C3—H3A	109.1	C12—C13—H13	120.3
C4—C3—H3B	109.1	C13—C14—C15	122.40 (18)
C2—C3—H3B	109.1	C13—C14—N1	118.70 (18)
H3A—C3—H3B	107.8	C15—C14—N1	118.90 (18)
C5—C4—C3	113.70 (17)	C16—C15—C14	118.02 (18)
C5—C4—H4A	108.8	C16—C15—H15	121.0
C3—C4—H4A	108.8	C14—C15—H15	121.0
C5—C4—H4B	108.8	C15—C16—C11	120.41 (18)
C3—C4—H4B	108.8	C15—C16—H16	119.8
H4A—C4—H4B	107.7	C11—C16—H16	119.8
C6—C5—C4	110.92 (17)

O1—C1—C2—C3	−173.95 (17)	C12—C13—C14—C15	0.9 (3)
C1—C2—C3—C4	179.61 (18)	C12—C13—C14—N1	−178.77 (17)
C2—C3—C4—C5	−178.18 (17)	O3—N1—C14—C13	164.72 (18)
C3—C4—C5—C6	179.28 (17)	O4—N1—C14—C13	−14.2 (3)
C11—O2—C6—C5	179.40 (16)	O3—N1—C14—C15	−14.9 (3)
C4—C5—C6—O2	−179.08 (16)	O4—N1—C14—C15	166.11 (19)
C6—O2—C11—C12	−1.1 (3)	C13—C14—C15—C16	−0.1 (3)
C6—O2—C11—C16	179.11 (16)	N1—C14—C15—C16	179.60 (18)
O2—C11—C12—C13	179.23 (18)	C14—C15—C16—C11	−1.3 (3)
C16—C11—C12—C13	−1.0 (3)	O2—C11—C16—C15	−178.36 (18)
C11—C12—C13—C14	−0.4 (3)	C12—C11—C16—C15	1.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.83 (5)	2.10 (5)	2.905 (2)	163 (4)

Symmetry code: (i) x−1, y+1, z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₇NO₄
M_r	239.27
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	5.4410 (7), 10.2270 (11), 11.3333 (14)
α, β, γ (°)	96.993 (9), 103.818 (10), 99.516 (10)
V (Å³)	595.34 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.24 × 0.12

Data collection
Diffractometer	STOE IPDS II two-circle- diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5002, 2105, 1694
R_int	0.074
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.185, 1.04
No. of reflections	2105
No. of parameters	159
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.33

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.83 (5)	2.10 (5)	2.905 (2)	163 (4)

Symmetry code: (i) x−1, y+1, z+1.

Acknowledgements

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

References

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