organic compounds
1,4-Bis(4-bromobutoxy)benzene
aDepartment of Physics, S.D.N.B. Vaishnav College for Women, Chromepet, Chennai 600 044, India, and bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
*Correspondence e-mail: lakssdnbvc@gmail.com
The complete molecule of the title compound, C14H20Br2O2, is generated by crystallographic inversion symmetry and the 4-bromobutoxy side chain adopts an extended conformation. In the crystal, weak C—H⋯π interactions are observed, which help to consolidate a herringbone packing motif.
Keywords: crystal structure; bromobutoxy; C—H⋯ π interactions.
CCDC reference: 1560690
Structure description
Compounds with alkyloxy substituents act as intermediates to engineer soluble electroluminescent oligomers and polymers for LED applications (Huang et al., 2007). As part of our studies in this area, we now describe the synthesis and structure of the title compound.
The x, 1 − y, −z] (Fig. 1). The bromoalkoxyl tail is roughly co-planar with the attached benzene ring with a C6—C5—O1—C4 torsion angle of −2.2 (3)°. The bromoalkoxyl tail adopts an extended conformation as shown by the C5—O1—C4—C3, O1—C4—C3—C2, C4—C3—C2—C1 and C3—C2—C1—Br1 torsion angles of −179.55 (19), −176.29 (18), 177.5 (2) and 179.19 (17)°, respectively. The packing of the molecules features weak C—H⋯π interactions (Table 1), which lead to a herringbone arrangement when viewed along [100] (Fig. 2).
contains one-half of the molecule, while the other half is generated through crystallographic inversion symmetry [symmetry code: (i) −Synthesis and crystallization
A mixture of (1.0 equiv.) of resorcinol and potassium carbonate (2.0 equiv.) in acetone (50 ml) was stirred for 15 minutes at 60° C. 1,4-Dibromobutane (2.1 equiv.) was added to the reaction mixture and stirred at 60° C for 7 h. After completion of the reaction, the solvent was removed under reduced pressure and the residue was extracted with CHCl3 (3 × 100 ml), washed with water (2 × 100 ml), brine (150 ml) and dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue obtained was purified by using CHCl3:hexane (1:9) as to afford the title compound as a white solid, which was recrystallized from methanol solution to yield colourless blocks.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1560690
https://doi.org/10.1107/S2414314617010045/hb4156sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617010045/hb4156Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617010045/hb4156Isup3.cml
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Bruno et al., 2002); software used to prepare material for publication: publCIF (Westrip, 2010).C14H20Br2O2 | F(000) = 380 |
Mr = 380.12 | Dx = 1.702 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0845 (10) Å | Cell parameters from 3047 reflections |
b = 5.3436 (5) Å | θ = 2.7–24.9° |
c = 15.3509 (15) Å | µ = 5.46 mm−1 |
β = 95.567 (4)° | T = 296 K |
V = 741.68 (13) Å3 | Block, colourless |
Z = 2 | 0.35 × 0.25 × 0.20 mm |
Bruker Kappa APEXII CCD diffractometer | 1310 independent reflections |
Radiation source: fine-focus sealed tube | 1126 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω and φ scan | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.525, Tmax = 0.745 | k = −6→6 |
7040 measured reflections | l = −18→18 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.052 | w = 1/[σ2(Fo2) + (0.0214P)2 + 0.4039P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
1310 reflections | Δρmax = 0.32 e Å−3 |
82 parameters | Δρmin = −0.33 e Å−3 |
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. H atoms were included in the refinement at calculated positions (C—H = 0.93–0.98 Å), with Uiso(H) = 1.2Ueq(C) using a riding-model approximation. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.0397 (3) | 1.4815 (5) | −0.34901 (18) | 0.0487 (7) | |
H1A | −0.1220 | 1.5707 | −0.3277 | 0.058* | |
H1B | −0.0796 | 1.3642 | −0.3934 | 0.058* | |
C2 | 0.0404 (3) | 1.3397 (4) | −0.27508 (15) | 0.0354 (6) | |
H2A | 0.0812 | 1.4561 | −0.2306 | 0.043* | |
H2B | 0.1216 | 1.2472 | −0.2962 | 0.043* | |
C3 | −0.0642 (3) | 1.1585 (4) | −0.23511 (15) | 0.0343 (6) | |
H3A | −0.1431 | 1.2523 | −0.2119 | 0.041* | |
H3B | −0.1085 | 1.0478 | −0.2804 | 0.041* | |
C4 | 0.0151 (3) | 1.0047 (4) | −0.16294 (15) | 0.0323 (5) | |
H4A | 0.0974 | 0.9162 | −0.1845 | 0.039* | |
H4B | 0.0532 | 1.1121 | −0.1150 | 0.039* | |
C5 | −0.0386 (3) | 0.6709 (4) | −0.06653 (14) | 0.0288 (5) | |
C6 | 0.1050 (3) | 0.6624 (4) | −0.02794 (15) | 0.0305 (5) | |
H6 | 0.1759 | 0.7708 | −0.0464 | 0.037* | |
C7 | 0.1431 (3) | 0.4919 (4) | 0.03832 (14) | 0.0307 (5) | |
H7 | 0.2399 | 0.4864 | 0.0642 | 0.037* | |
O1 | −0.08882 (18) | 0.8306 (3) | −0.13368 (11) | 0.0376 (4) | |
Br1 | 0.08821 (3) | 1.72008 (5) | −0.40166 (2) | 0.04831 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0408 (17) | 0.0559 (16) | 0.0491 (16) | −0.0108 (13) | 0.0028 (13) | 0.0206 (13) |
C2 | 0.0386 (15) | 0.0339 (12) | 0.0338 (13) | −0.0018 (11) | 0.0035 (11) | 0.0026 (10) |
C3 | 0.0347 (15) | 0.0358 (13) | 0.0324 (13) | −0.0015 (11) | 0.0027 (11) | 0.0056 (10) |
C4 | 0.0335 (14) | 0.0322 (12) | 0.0314 (12) | −0.0024 (10) | 0.0038 (11) | 0.0037 (10) |
C5 | 0.0323 (13) | 0.0283 (11) | 0.0256 (12) | 0.0017 (10) | 0.0021 (10) | 0.0006 (9) |
C6 | 0.0274 (13) | 0.0322 (12) | 0.0321 (12) | −0.0037 (10) | 0.0035 (10) | 0.0028 (10) |
C7 | 0.0248 (13) | 0.0353 (12) | 0.0313 (12) | −0.0012 (10) | −0.0001 (10) | 0.0015 (10) |
O1 | 0.0323 (10) | 0.0402 (9) | 0.0390 (9) | −0.0043 (8) | −0.0022 (8) | 0.0147 (8) |
Br1 | 0.0566 (2) | 0.04394 (17) | 0.04603 (18) | −0.00749 (13) | 0.01338 (13) | 0.01054 (12) |
C1—C2 | 1.494 (3) | C4—O1 | 1.428 (3) |
C1—Br1 | 1.952 (2) | C4—H4A | 0.9700 |
C1—H1A | 0.9700 | C4—H4B | 0.9700 |
C1—H1B | 0.9700 | C5—C6 | 1.381 (3) |
C2—C3 | 1.526 (3) | C5—O1 | 1.381 (3) |
C2—H2A | 0.9700 | C5—C7i | 1.387 (3) |
C2—H2B | 0.9700 | C6—C7 | 1.384 (3) |
C3—C4 | 1.506 (3) | C6—H6 | 0.9300 |
C3—H3A | 0.9700 | C7—C5i | 1.387 (3) |
C3—H3B | 0.9700 | C7—H7 | 0.9300 |
C2—C1—Br1 | 112.34 (19) | H3A—C3—H3B | 107.9 |
C2—C1—H1A | 109.1 | O1—C4—C3 | 107.66 (19) |
Br1—C1—H1A | 109.1 | O1—C4—H4A | 110.2 |
C2—C1—H1B | 109.1 | C3—C4—H4A | 110.2 |
Br1—C1—H1B | 109.1 | O1—C4—H4B | 110.2 |
H1A—C1—H1B | 107.9 | C3—C4—H4B | 110.2 |
C1—C2—C3 | 110.6 (2) | H4A—C4—H4B | 108.5 |
C1—C2—H2A | 109.5 | C6—C5—O1 | 124.8 (2) |
C3—C2—H2A | 109.5 | C6—C5—C7i | 119.5 (2) |
C1—C2—H2B | 109.5 | O1—C5—C7i | 115.7 (2) |
C3—C2—H2B | 109.5 | C5—C6—C7 | 119.7 (2) |
H2A—C2—H2B | 108.1 | C5—C6—H6 | 120.2 |
C4—C3—C2 | 111.7 (2) | C7—C6—H6 | 120.2 |
C4—C3—H3A | 109.3 | C6—C7—C5i | 120.8 (2) |
C2—C3—H3A | 109.3 | C6—C7—H7 | 119.6 |
C4—C3—H3B | 109.3 | C5i—C7—H7 | 119.6 |
C2—C3—H3B | 109.3 | C5—O1—C4 | 117.18 (18) |
Br1—C1—C2—C3 | 179.19 (17) | C5—C6—C7—C5i | 0.0 (4) |
C1—C2—C3—C4 | 177.5 (2) | C6—C5—O1—C4 | −2.2 (3) |
C2—C3—C4—O1 | −176.29 (18) | C7i—C5—O1—C4 | 178.59 (18) |
O1—C5—C6—C7 | −179.2 (2) | C3—C4—O1—C5 | −179.55 (19) |
C7i—C5—C6—C7 | 0.0 (4) |
Symmetry code: (i) −x, −y+1, −z. |
Cg1 is the centroid of the benzene ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2B···Cg1ii | 0.97 | 2.84 | 3.664 (3) | 144 |
Symmetry code: (ii) x−1/2, −y−1/2, z−3/2. |
Acknowledgements
The authors thank the single-crystal XRD facility, SAIF IIT Madras, Chennai, for the data collection.
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