1,4-Bis(2-nitro­phen­oxy)butane

Elizondo, P.; Rodríguez de Barbarín, C.; Nájera, B.; Pérez, N.

doi:10.1107/S1600536809048909

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3217

doi:10.1107/S1600536809048909

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1,4-Bis(2-nitrophenoxy)butane

Perla Elizondo,^a Cecilia Rodríguez de Barbarín,^a ^* Blanca Nájera ^a and Nancy Pérez ^a

^aDivisión de Estudios de Posgrado, Facultad de Ciencias Químicas, Universidad Autónoma de Nuevo León, AP 1864, 64570 Monterrey, NL, Mexico
^*Correspondence e-mail: cecybarbarin@yahoo.com

(Received 21 October 2009; accepted 17 November 2009; online 25 November 2009)

The asymmetric unit of the title compound, C₁₆H₁₆N₂O₆, contains one-half molecule, the mid-point of the central C—C bond being located on a crystallographic inversion center. The crystal structure shows weak interactions between the O atoms of the nitro groups and two different C—H groups of the benzene rings. The extended weak hydrogen-bond formation, involving the NO₂ groups, generates an infinite three-dimensional network.

Related literature

For related structures, see: Han & Zhen (2005 ); Naz et al. (2007 ); Zhang et al. (2007 ). For recent examples of complexes with macrocyclic ligands, including diether subunits, see: Fernández et al. (2008 ); Platas-Iglesias et al. (2005 ); Tas et al. (2006 ).

Experimental

Crystal data

C₁₆H₁₆N₂O₆
M_r = 332.31
Monoclinic, P 2₁ /c
a = 7.7977 (8) Å
b = 13.888 (2) Å
c = 7.6729 (8) Å
β = 110.866 (6)°
V = 776.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.7 × 0.6 × 0.4 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
3850 measured reflections
2256 independent reflections
1752 reflections with I > 2σ(I)
R_int = 0.030
3 standard reflections every 97 reflections intensity decay: 2.3%

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.130
S = 1.06
2256 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O1ⁱ	0.93	2.63	3.284 (2)	128
C5—H5A⋯O2ⁱⁱ	0.93	2.58	3.476 (2)	163
Symmetry codes: (i) x+1, y, z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x, -y, -z+1.

Data collection: XSCANS (Siemens, 1996 ); cell refinement: XSCANS; data reduction: SHELXTL-Plus (Sheldrick, 2008 ); program(s) used to solve structure: SHELXTL-Plus; program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL-Plus.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809048909/im2156sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048909/im2156Isup2.hkl

checkCIF report

Comment top

The title compound (I) has been synthesized as a chemical precursor of a variety of acyclic and macrocyclic multidentate ligands and metal complexes.

Related compounds have been reported (Zhang et al., 2007; Naz et al., 2007 and Han & Zhen, 2005). Similar cyclic and macrocyclic ligands to (I), have been reported (Fernández et al., 2008; Tas et al., 2006 and Platas-Iglesias et al., 2005).

Compound (I) crystallizes with the molecule being situated on a crystallographic inversion center that is localized at the midpoint of the C8—C8ⁱ bond [symmetry code: (i) -x, -y, -z + 1] (Fig. 1). As a consequence of the centrosymmetric nature of the molecule a dihedral angle of 0° is observed between the benzene rings in (I). The torsion angle between a benzene ring and the corresponding nitro group is 38.5 (1)°. The conformation of the central chain is described by torsion angles, C6—O3—C7—C8, -178.2 (1)°, O3—C7—C8—C8ⁱ, 62.6 (2)° and C7—C8—C8ⁱ—C7ⁱ, constrained by symmetry to 180.0°. This trans-gauche-trans conformation stabilized in the solid state for (I) is less common than the all-trans conformation that is generally found in aliphatic systems. This molecular conformation is stabilized by weak intramolecular hydrogen bonds involving O3 and a symmetry related C—H group (O3···H8B 2.900 (2) Å). Nevertheless, O atoms in (I) may coordinate to a metal center as a chelating ligand after changing the conformation of this potential ligand. These observations suggest that (I) is a highly flexible molecule, with an almost free rotation about all σ bonds.

In addition, the crystal structure shows weak interactions between oxygen atoms of the nitro groups and two different C—H groups of benzene rings (O1···H3A 2.627 and O2···H5A 2.577 Å) as shown in Fig 2. The extended weak H bond formation, using the NO₂ groups, produces an infinite three-dimensional network of the title compound.

Related literature top

For related structures, see: Han & Zhen (2005); Naz et al. (2007); Zhang et al. (2007). For recent examples of complexes with macrocyclic ligands, including diether subunits, see: Fernández et al. (2008); Platas-Iglesias et al. (2005); Tas et al. (2006).

Experimental top

o-Nitrophenol (23.90 g) in hot DMF (25.0 ml) was treated with potassium carbonate (11.90 g), added slowly in portions. The solution was gently boiled and 1,4-dibromobutane (8.40 ml) was added during 30 min. Gentle reflux was mantained for another 2 h. Then solvent (15.0 ml) was destilled from the mixture and the remaining mixture was poured into water (250 ml). The granular yellow solid was filtered off, washed with dilute aqueous sodium hydroxide solution and water, then dried (23.8 g). M.p. 442–443 K, yield 81%.

Suitable crystals were obtained as colorless blocks from acetonitrile solution by slow evaporation of the solvent at 298 K. The solid was characterized by IR (KBr disc), ¹H-NMR and elemental analysis, which are in agreement with the X-ray structure.

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: SHELXTL-Plus (Sheldrick, 2008); program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-Plus (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. Atoms not labelled are related to the asymmetric unit by symmetry code -x, -y, -z + 1.
	Fig. 2. Molecular packing structure of (I) showing week interactions between O of the nitro groups and H atoms of two different C—H groups of the benzene rings (dashed bonds). H atoms not involved in this network have been omitted.

1,4-Bis(2-nitrophenoxy)butane top

Crystal data top

C₁₆H₁₆N₂O₆	F(000) = 348
M_r = 332.31	D_x = 1.421 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 442–443 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.7977 (8) Å	Cell parameters from 85 reflections
b = 13.888 (2) Å	θ = 5.2–12.4°
c = 7.6729 (8) Å	µ = 0.11 mm⁻¹
β = 110.866 (6)°	T = 296 K
V = 776.4 (2) Å³	Block, colorless
Z = 2	0.7 × 0.6 × 0.4 mm

Data collection top

Bruker P4 diffractometer	R_int = 0.030
Radiation source: fine-focus sealed tube	θ_max = 30.0°, θ_min = 2.9°
Graphite monochromator	h = −10→10
ω scan	k = −1→19
3850 measured reflections	l = −10→5
2256 independent reflections	3 standard reflections every 97 reflections
1752 reflections with I > 2σ(I)	intensity decay: 2.3%

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0452P)² + 0.1839P] where P = (F_o² + 2F_c²)/3
2256 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₆H₁₆N₂O₆	V = 776.4 (2) Å³
M_r = 332.31	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7977 (8) Å	µ = 0.11 mm⁻¹
b = 13.888 (2) Å	T = 296 K
c = 7.6729 (8) Å	0.7 × 0.6 × 0.4 mm
β = 110.866 (6)°

Data collection top

Bruker P4 diffractometer	R_int = 0.030
3850 measured reflections	3 standard reflections every 97 reflections
2256 independent reflections	intensity decay: 2.3%
1752 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.06	Δρ_max = 0.22 e Å⁻³
2256 reflections	Δρ_min = −0.19 e Å⁻³
110 parameters

Special details top

Experimental. Experimental absorption correction were not applied because the molecule is purely organic, and no better structure refinement was obtained.

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
O1	0.19481 (19)	0.21566 (10)	0.9250 (3)	0.0923 (5)
O2	0.32880 (19)	0.33983 (9)	0.8740 (2)	0.0827 (4)
O3	0.28310 (12)	0.07009 (6)	0.74649 (13)	0.0474 (3)
N1	0.32195 (16)	0.25370 (9)	0.89929 (17)	0.0506 (3)
C1	0.47947 (16)	0.19562 (9)	0.90340 (16)	0.0392 (3)
C2	0.65074 (18)	0.23662 (10)	0.98583 (19)	0.0487 (3)
H2A	0.6618	0.2979	1.0376	0.058*
C3	0.80442 (19)	0.18694 (12)	0.9912 (2)	0.0575 (4)
H3A	0.9205	0.2136	1.0478	0.069*
C4	0.7837 (2)	0.09688 (12)	0.9114 (2)	0.0579 (4)
H4A	0.8874	0.0634	0.9126	0.070*
C5	0.61331 (19)	0.05505 (10)	0.8296 (2)	0.0497 (3)
H5A	0.6038	−0.0060	0.7772	0.060*
C6	0.45534 (16)	0.10362 (9)	0.82495 (16)	0.0388 (3)
C7	0.2563 (2)	−0.01938 (9)	0.6464 (2)	0.0495 (3)
H7A	0.3192	−0.0712	0.7294	0.059*
H7B	0.3044	−0.0151	0.5462	0.059*
C8	0.0531 (2)	−0.03792 (10)	0.5688 (2)	0.0534 (4)
H8A	0.0081	−0.0418	0.6699	0.064*
H8B	0.0315	−0.0991	0.5063	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0717 (8)	0.0766 (9)	0.1558 (14)	−0.0089 (7)	0.0739 (9)	−0.0235 (9)
O2	0.0880 (9)	0.0461 (6)	0.1202 (12)	0.0135 (6)	0.0448 (8)	0.0006 (7)
O3	0.0423 (5)	0.0429 (5)	0.0527 (5)	−0.0051 (4)	0.0117 (4)	−0.0121 (4)
N1	0.0481 (6)	0.0500 (6)	0.0554 (7)	−0.0005 (5)	0.0205 (5)	−0.0119 (5)
C1	0.0392 (6)	0.0400 (6)	0.0386 (6)	−0.0007 (4)	0.0142 (5)	−0.0014 (5)
C2	0.0467 (7)	0.0481 (7)	0.0479 (7)	−0.0098 (5)	0.0125 (5)	−0.0025 (5)
C3	0.0388 (6)	0.0690 (9)	0.0584 (8)	−0.0073 (6)	0.0098 (6)	0.0055 (7)
C4	0.0425 (7)	0.0699 (9)	0.0606 (9)	0.0146 (6)	0.0174 (6)	0.0126 (7)
C5	0.0506 (7)	0.0459 (7)	0.0510 (7)	0.0100 (5)	0.0160 (6)	0.0012 (6)
C6	0.0393 (6)	0.0388 (6)	0.0365 (5)	−0.0013 (4)	0.0111 (4)	0.0003 (4)
C7	0.0574 (8)	0.0354 (6)	0.0501 (7)	−0.0045 (5)	0.0122 (6)	−0.0054 (5)
C8	0.0603 (8)	0.0385 (6)	0.0520 (8)	−0.0123 (6)	0.0085 (6)	0.0006 (5)

Geometric parameters (Å, º) top

O1—N1	1.2000 (16)	C4—C5	1.380 (2)
O2—N1	1.2159 (17)	C4—H4A	0.9300
O3—C6	1.3443 (15)	C5—C6	1.3937 (18)
O3—C7	1.4363 (15)	C5—H5A	0.9300
N1—C1	1.4604 (16)	C7—C8	1.504 (2)
C1—C2	1.3807 (17)	C7—H7A	0.9700
C1—C6	1.3962 (17)	C7—H7B	0.9700
C2—C3	1.371 (2)	C8—C8ⁱ	1.512 (3)
C2—H2A	0.9300	C8—H8A	0.9600
C3—C4	1.377 (2)	C8—H8B	0.9601
C3—H3A	0.9300

C6—O3—C7	118.09 (10)	C4—C5—H5A	119.8
O1—N1—O2	123.04 (14)	C6—C5—H5A	119.8
O1—N1—C1	119.40 (13)	O3—C6—C5	125.22 (12)
O2—N1—C1	117.54 (12)	O3—C6—C1	118.02 (11)
C2—C1—C6	122.32 (11)	C5—C6—C1	116.73 (11)
C2—C1—N1	116.81 (11)	O3—C7—C8	106.96 (11)
C6—C1—N1	120.86 (11)	O3—C7—H7A	110.3
C3—C2—C1	119.93 (13)	C8—C7—H7A	110.3
C3—C2—H2A	120.0	O3—C7—H7B	110.3
C1—C2—H2A	120.0	C8—C7—H7B	110.3
C2—C3—C4	118.77 (13)	H7A—C7—H7B	108.6
C2—C3—H3A	120.6	C7—C8—C8ⁱ	113.25 (14)
C4—C3—H3A	120.6	C7—C8—H8A	109.1
C3—C4—C5	121.74 (13)	C8ⁱ—C8—H8A	109.7
C3—C4—H4A	119.1	C7—C8—H8B	108.7
C5—C4—H4A	119.1	C8ⁱ—C8—H8B	108.2
C4—C5—C6	120.48 (13)	H8A—C8—H8B	107.7

O1—N1—C1—C2	−141.19 (16)	C7—O3—C6—C1	172.71 (11)
O2—N1—C1—C2	37.07 (18)	C4—C5—C6—O3	178.93 (13)
O1—N1—C1—C6	39.59 (19)	C4—C5—C6—C1	1.0 (2)
O2—N1—C1—C6	−142.15 (14)	C2—C1—C6—O3	−179.48 (12)
C6—C1—C2—C3	0.5 (2)	N1—C1—C6—O3	−0.30 (17)
N1—C1—C2—C3	−178.69 (13)	C2—C1—C6—C5	−1.43 (18)
C1—C2—C3—C4	0.8 (2)	N1—C1—C6—C5	177.75 (12)
C2—C3—C4—C5	−1.2 (2)	C6—O3—C7—C8	−178.18 (11)
C3—C4—C5—C6	0.2 (2)	O3—C7—C8—C8ⁱ	62.6 (2)
C7—O3—C6—C5	−5.15 (19)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O1ⁱⁱ	0.93	2.63	3.284 (2)	128
C5—H5A···O2ⁱⁱⁱ	0.93	2.58	3.476 (2)	163
C8—H8B···O3ⁱ	0.96	2.56	2.900 (2)	101

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₂O₆
M_r	332.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.7977 (8), 13.888 (2), 7.6729 (8)
β (°)	110.866 (6)
V (Å³)	776.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.7 × 0.6 × 0.4

Data collection
Diffractometer	Bruker P4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3850, 2256, 1752
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.130, 1.06
No. of reflections	2256
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.19

Computer programs: XSCANS (Siemens, 1996), SHELXTL-Plus (Sheldrick, 2008) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O1ⁱ	0.93	2.63	3.284 (2)	128
C5—H5A···O2ⁱⁱ	0.93	2.58	3.476 (2)	163
C8—H8B···O3ⁱⁱⁱ	0.96	2.56	2.900 (2)	101

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

Acknowledgements

The authors thank the PAICYT of the UANL for support of this work [project Number CA-1260–06].

References

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