supplementary materials


hg5309 scheme

Acta Cryst. (2013). E69, o793    [ doi:10.1107/S1600536813010830 ]

4-Formyl-2-nitrophenyl 4-bromobenzoate

R. Moreno-Fuquen, G. Hernandez, J. Ellena, C. A. De Simone and J. C. Tenorio

Abstract top

In the title compound, C14H8BrNO5, the benzene rings form a dihedral angle of 62.90 (7)°. The central ester group is twisted away from the nitro-substituted and bromo-substituted rings by 71.67 (7) and 8.78 (15)°, respectively. The nitro group forms a dihedral angle of 7.77 (16)° with the benzene ring to which it is attached. In the crystal, molecules are linked by weak C-H...O interactions, forming C(12) chains which run along [001]. Halogen-halogen interactions [Br...Br = 3.523 (3) Å] within the chains stabilized by C-H...O interactions are observed.

Comment top

Esters containing aromatic nitro-substituted rings can be used as precursors for the preparation of compounds with potential analgesic and anti-inflammatory properties (Jefford & Zaslona, 1985). Indeed, many pharmaceuticals come from a variety of nitroaromatic compounds. Acetaminophen for example, a widely used drug, is sinthesized from p-nitrophenol (Bhattacharya et al., 2006). Other nitro-aromatic esters show marked inhibitory activity against ischemic-induced electrocardiographic changes (Benedini et al., 1995). In order to complement the structural information about nitroaryl compounds the title ester, 4-formyl-2-nitrophenyl 4-bromo benzoate, (I), was synthesized. The molecular structure of (I) is shown in Fig. 1. Bond lengths and bond angles in (I), show marked similarity with other aryl benzoates reported in the literature such as 4-methylphenyl 4-bromobenzoate (MPBrB) (Moreno-Fuquen et al., 2011), 4-nitrophenyl 4-bromobenzoate (NPBrB) (Moreno-Fuquen, 2011) and 2,4,6-trinitrophenyl-4-chlorobenzoate (TNPClB) (Moreno-Fuquen et al., 2013). However, it was noticed in (I) that the bond length O4-C1 in the ester moety, is shortened if it is compared with analogous distances in systems like MPBrB, NPBrB and the majority of similar aromatic esters. This behavior is comparable with those ones well described for trinitro-phenyl benzoates, such as TNPClB, as a consequence of resonance effects over the structure, prominently caused for ortho-nitro-substitution. The benzene rings of (I) form a dihedral angle of 62.90 (7)°, a value close to the value presented in TNPClB and NPBrB systems [63.46 (5)° and 64.98 (10)°] respectively. The ester group is twisted away from the nitro-substituted and bromo-substituted benzene rings by 71.67 (7)° and 8.78 (15)° respectively. The nitro group forms a dihedral angle with the benzene ring to which it is attached of 7.77 (16)°.

The crystal packing shows no classical hydrogen bonds and it is stabilized by weak C-H···O intermolecular interactions, forming C(12) chains along [001] (see Fig. 2; Etter, 1990). The C13 atom of the benzoic ring at (x,y,z) acts as hydrogen-bond donors to O1 atom at (x,-y+1/2,+z-1/2) (see Table 1; Nardelli, 1995).

Recent theoretical calculations show that halogen···halogen interactions are controlled by electrostatic forces and they display directional character (Awwadi et al., 2006). In the title structure, halogen···halogen interactions [Br···Br = 3.523 (3) Å] within the chains stabilized by C—H···O interactions are observed. This Br···Br distance is much shorter than the sum of the van der Waals radii (3.70 Å) (Bondi, 1964). These interactions can be considered type I with trans geometry (Hathwar et al., 2010).

Related literature top

For medicinal and pharmaceutical properties of nitroaromatic compounds, see: Jefford & Zaslona (1985); Bhattacharya et al. (2006); Benedini et al. (1995); For similar structures, see: Moreno-Fuquen et al. (2011, 2013); Moreno-Fuquen (2011). For van der Waals radii, see: Bondi (1964). For halogen–halogen interactions see Awwadi et al. (2006); Hathwar et al. (2010). For hydrogen bonding, see: Etter (1990); Nardelli (1995).

Experimental top

The reagents and solvents for the synthesis were obtained from the Aldrich Chemical Co., and were used without additional purification. In a 100 ml round bottom flask 4-hydroxy-3-nitrobenzaldehyde (0.571 mmol, 0.20 g) and 4-bromobenzoyl chloride in equimolar amounts, were dissolved in 20 mL of acetonitrile. Also a few drops of pyridine were added. Then the mixture was left to reflux in constant stirring for about two hours. A colourless solid was obtained after leaving the solvent to evaporate. IR spectra were recorded on a FT-IR SHIMADZU IR-Affinity-1 spectrophotometer. Colourless crystals; m.p 422 (1)K. IR (KBr) 3101.90 cm-1, 3072.12 cm-1 (aromatic C-H); 1741.61 cm-1 (benzaldehyde C=O); 1710.5 cm-1 (ester C=O), 1228.04 cm-1 (ester C-O); 1533.35 cm-1, 1339.51 cm-1 (nitro –NO2); 1072.81 cm-1 (C=C); 742.43 cm-1(Br-C).

Refinement top

All the H-atoms attached to C atoms were positioned at geometrically idealized positions and treated as riding with C—H= 0.96 Å and Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. Molecular conformation and atom numbering scheme for the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the formation of chains which running along [001]. Symmetry code: (i) x,-y+1/2,+z-1/2.
4-Formyl-2-nitrophenyl 4-bromobenzoate top
Crystal data top
C14H8BrNO5F(000) = 696
Mr = 350.12Dx = 1.731 Mg m3
Monoclinic, P21/cMelting point: 422(1) K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 6.5308 (2) ÅCell parameters from 3737 reflections
b = 8.2253 (2) Åθ = 3.0–26.4°
c = 25.6860 (8) ŵ = 3.08 mm1
β = 103.1910 (9)°T = 295 K
V = 1343.38 (7) Å3Prism, colourless
Z = 40.38 × 0.16 × 0.12 mm
Data collection top
Nonius KappaCCD
diffractometer
2746 independent reflections
Radiation source: fine-focus sealed tube2095 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.086
CCD rotation images, thick slices scansθmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 86
Tmin = 0.568, Tmax = 0.687k = 109
16446 measured reflectionsl = 3232
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0507P)2 + 0.4984P]
where P = (Fo2 + 2Fc2)/3
2746 reflections(Δ/σ)max < 0.001
190 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
C14H8BrNO5V = 1343.38 (7) Å3
Mr = 350.12Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.5308 (2) ŵ = 3.08 mm1
b = 8.2253 (2) ÅT = 295 K
c = 25.6860 (8) Å0.38 × 0.16 × 0.12 mm
β = 103.1910 (9)°
Data collection top
Nonius KappaCCD
diffractometer
2746 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2095 reflections with I > 2σ(I)
Tmin = 0.568, Tmax = 0.687Rint = 0.086
16446 measured reflectionsθmax = 26.4°
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.113Δρmax = 0.43 e Å3
S = 1.03Δρmin = 0.39 e Å3
2746 reflectionsAbsolute structure: ?
190 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Br11.31938 (6)0.42327 (5)0.035355 (14)0.08659 (19)
O10.7475 (5)0.4084 (3)0.49383 (11)0.0950 (8)
O21.3030 (4)0.2431 (3)0.40032 (11)0.0952 (8)
N11.1928 (4)0.2760 (3)0.35705 (11)0.0598 (6)
C10.8918 (4)0.4497 (3)0.31011 (11)0.0499 (6)
C20.7088 (4)0.5329 (3)0.31062 (12)0.0587 (7)
H20.63590.58900.27900.070*
C30.6341 (5)0.5347 (3)0.35660 (12)0.0600 (7)
H30.50510.59090.35630.072*
C40.7415 (4)0.4571 (3)0.40263 (11)0.0542 (6)
C50.9260 (4)0.3742 (3)0.40244 (10)0.0509 (6)
H51.00400.32050.43390.061*
C60.9988 (4)0.3692 (3)0.35613 (11)0.0487 (6)
O31.2303 (4)0.2336 (3)0.31487 (10)0.0826 (7)
O40.9767 (3)0.4597 (2)0.26543 (7)0.0585 (5)
O50.7279 (3)0.2919 (2)0.21998 (8)0.0638 (5)
C70.6609 (5)0.4666 (4)0.45221 (12)0.0622 (7)
H70.53320.52500.45180.075*
C80.8811 (4)0.3721 (3)0.22136 (10)0.0495 (6)
C90.9929 (4)0.3918 (3)0.17757 (10)0.0472 (6)
C101.1847 (4)0.4683 (3)0.18437 (11)0.0525 (6)
H101.25020.51400.21850.063*
C111.2847 (4)0.4808 (3)0.14219 (12)0.0575 (7)
H111.41900.53290.14630.069*
C121.1860 (5)0.4152 (3)0.09351 (11)0.0557 (7)
C130.9933 (5)0.3400 (4)0.08568 (12)0.0630 (7)
H130.92830.29610.05120.076*
C140.8966 (4)0.3285 (3)0.12789 (11)0.0576 (7)
H140.76170.27690.12310.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0923 (3)0.1169 (4)0.0618 (3)0.00649 (19)0.0410 (2)0.00527 (18)
O10.112 (2)0.121 (2)0.0613 (17)0.0260 (15)0.0380 (15)0.0109 (14)
O20.0753 (14)0.133 (2)0.0756 (17)0.0367 (14)0.0142 (13)0.0138 (15)
N10.0586 (13)0.0586 (13)0.0649 (16)0.0002 (10)0.0197 (12)0.0011 (12)
C10.0572 (15)0.0541 (14)0.0397 (14)0.0125 (11)0.0138 (11)0.0027 (11)
C20.0602 (16)0.0662 (16)0.0492 (16)0.0020 (13)0.0113 (13)0.0072 (13)
C30.0592 (16)0.0650 (17)0.0578 (18)0.0083 (13)0.0171 (14)0.0017 (14)
C40.0619 (16)0.0555 (15)0.0495 (16)0.0002 (12)0.0217 (13)0.0024 (12)
C50.0609 (16)0.0520 (13)0.0407 (14)0.0010 (12)0.0138 (12)0.0011 (11)
C60.0511 (14)0.0451 (12)0.0525 (15)0.0026 (11)0.0168 (12)0.0029 (11)
O30.0878 (15)0.0896 (15)0.0811 (16)0.0140 (12)0.0415 (13)0.0103 (13)
O40.0624 (11)0.0732 (12)0.0424 (11)0.0174 (9)0.0169 (9)0.0027 (9)
O50.0610 (11)0.0761 (12)0.0576 (12)0.0208 (10)0.0202 (9)0.0045 (9)
C70.078 (2)0.0668 (17)0.0487 (17)0.0074 (14)0.0293 (15)0.0008 (14)
C80.0528 (15)0.0511 (13)0.0439 (14)0.0011 (12)0.0096 (11)0.0023 (11)
C90.0505 (14)0.0475 (13)0.0444 (14)0.0002 (10)0.0125 (11)0.0026 (11)
C100.0539 (15)0.0569 (14)0.0460 (15)0.0046 (12)0.0101 (12)0.0037 (12)
C110.0564 (15)0.0607 (16)0.0581 (18)0.0075 (13)0.0184 (13)0.0011 (13)
C120.0646 (16)0.0621 (16)0.0442 (15)0.0054 (13)0.0205 (13)0.0077 (12)
C130.0703 (18)0.0736 (18)0.0439 (15)0.0067 (15)0.0104 (13)0.0018 (13)
C140.0554 (15)0.0690 (17)0.0479 (16)0.0100 (13)0.0105 (12)0.0014 (13)
Geometric parameters (Å, º) top
Br1—C121.894 (3)C5—H50.9601
O1—C71.190 (4)O4—C81.367 (3)
O2—N11.209 (3)O5—C81.192 (3)
N1—O31.215 (3)C7—H70.9599
N1—C61.476 (3)C8—C91.483 (3)
C1—C21.380 (4)C9—C101.377 (4)
C1—O41.386 (3)C9—C141.389 (4)
C1—C61.395 (4)C10—C111.391 (4)
C2—C31.377 (4)C10—H100.9599
C2—H20.9599C11—C121.380 (4)
C3—C41.385 (4)C11—H110.9600
C3—H30.9600C12—C131.375 (4)
C4—C51.385 (4)C13—C141.377 (4)
C4—C71.487 (4)C13—H130.9601
C5—C61.379 (3)C14—H140.9600
O2—N1—O3123.8 (3)O1—C7—H7116.4
O2—N1—C6117.4 (2)C4—C7—H7119.5
O3—N1—C6118.8 (2)O5—C8—O4122.6 (2)
C2—C1—O4119.3 (2)O5—C8—C9126.4 (2)
C2—C1—C6119.7 (3)O4—C8—C9111.1 (2)
O4—C1—C6120.8 (2)C10—C9—C14119.7 (2)
C3—C2—C1119.4 (3)C10—C9—C8123.0 (2)
C3—C2—H2121.0C14—C9—C8117.2 (2)
C1—C2—H2119.6C9—C10—C11120.7 (3)
C2—C3—C4121.2 (3)C9—C10—H10119.8
C2—C3—H3118.8C11—C10—H10119.5
C4—C3—H3120.0C12—C11—C10118.1 (2)
C3—C4—C5119.7 (3)C12—C11—H11120.0
C3—C4—C7119.9 (3)C10—C11—H11121.8
C5—C4—C7120.5 (3)C13—C12—C11122.1 (3)
C6—C5—C4119.3 (2)C13—C12—Br1118.1 (2)
C6—C5—H5119.5C11—C12—Br1119.8 (2)
C4—C5—H5121.2C12—C13—C14119.0 (3)
C5—C6—C1120.8 (2)C12—C13—H13120.1
C5—C6—N1117.8 (2)C14—C13—H13120.9
C1—C6—N1121.5 (2)C13—C14—C9120.3 (3)
C8—O4—C1117.44 (19)C13—C14—H14120.1
O1—C7—C4124.0 (3)C9—C14—H14119.6
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O1i0.962.373.254 (4)153
Symmetry code: (i) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O1i0.962.373.254 (4)153.4
Symmetry code: (i) x, y+1/2, z1/2.
Acknowledgements top

RMF is grateful to the Spanish Research Council (CSIC) for the use of a free-of-charge licence to the Cambridge Structural Database. RMF also thanks the Universidad del Valle, Colombia, for partial financial support.

references
References top

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