organic compounds
4-Bromo-4′-(dimethylamino)stilbene
aDepartamento de Química – Facultad de Ciencias, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, and bWestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland
*Correspondence e-mail: rodimo26@yahoo.es
In the title compound, C16H16BrN, the benzene rings are inclined to each other with a dihedral angle between their mean planes of 50.5 (3)° and the C=C bond adopts a cis conformation.
Related literature
For background information on photonic materials, see: He et al. (2008). For related systems of stilbene, see: Moreno-Fuquen et al. (2008, 2009). For literature related to the synthesis, see: Maryanoff & Reitz (1989).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; 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, 1997); software used to prepare material for publication: PARST95 (Nardelli, 1995).
Supporting information
10.1107/S1600536809020492/hg2518sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809020492/hg2518Isup2.hkl
By means of Wittig reaction (Maryanoff & Reitz, 1989), the 4-dimethylamino-benzyl-triphenylphosphonium iodide was prepared. The title stilbene was obtained by the reaction of equimolar quantities of phosphonium salt and 4-bromo benzaldehyde (0.03 mol) in THF solution. The mixture was maintained with stirring under argon atmosphere. The reaction mixture was kept at 273 K and it was dropped with a solution of tert-butanol and potassium tert-butoxide. Crystals of medium quality but suitable for single-crystal X-ray diffraction were grown in chloroform. An attempt was made to improve the quality of the crystals without success. Thin layer
(TLC) was used to confirm the structure of the individual compounds. IR spectra were recorded on a Shimadzu FT—IR 8400 spectrophotometer.N-(p-chlorophenyl)maleimide. Yellow crystals; yield 60%; mp 354 (1) K. IR (KBr) 2884 cm-1 (C—H), 3433 cm-1 (=C—H), 1609 cm-1 (C=C), 815 cm-1 (C=Br).
All H-atoms were located from difference maps and then they were treated as riding atoms [Caro—H= 0.93 A° and Csp3—H= 0.96 A°, Uiso(H)= 1.2Ueq(Caro), Uiso(H)= 1.5Ueq(Csp3)).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007; 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, 1997); software used to prepare material for publication: PARST95 (Nardelli, 1995).C16H16BrN | F(000) = 616 |
Mr = 302.21 | Dx = 1.469 Mg m−3 |
Monoclinic, P21/c | Melting point: 354(1) K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 14.804 (2) Å | Cell parameters from 2824 reflections |
b = 6.0962 (5) Å | θ = 2.7–29.0° |
c = 15.2106 (10) Å | µ = 2.99 mm−1 |
β = 95.331 (9)° | T = 123 K |
V = 1366.8 (2) Å3 | Slab, yellow |
Z = 4 | 0.38 × 0.25 × 0.10 mm |
Bruker APEXII CCD diffractometer | 2986 independent reflections |
Radiation source: fine-focus sealed tube | 1533 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ϕ and ω scans | θmax = 27.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −18→18 |
Tmin = 0.457, Tmax = 0.749 | k = −7→7 |
8606 measured reflections | l = −19→19 |
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)] = 0.075 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.213 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.1119P)2] where P = (Fo2 + 2Fc2)/3 |
2986 reflections | (Δ/σ)max < 0.001 |
165 parameters | Δρmax = 0.94 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
C16H16BrN | V = 1366.8 (2) Å3 |
Mr = 302.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.804 (2) Å | µ = 2.99 mm−1 |
b = 6.0962 (5) Å | T = 123 K |
c = 15.2106 (10) Å | 0.38 × 0.25 × 0.10 mm |
β = 95.331 (9)° |
Bruker APEXII CCD diffractometer | 2986 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 1533 reflections with I > 2σ(I) |
Tmin = 0.457, Tmax = 0.749 | Rint = 0.064 |
8606 measured reflections |
R[F2 > 2σ(F2)] = 0.075 | 0 restraints |
wR(F2) = 0.213 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.94 e Å−3 |
2986 reflections | Δρmin = −0.54 e Å−3 |
165 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.36239 (6) | −0.41740 (14) | 0.35579 (5) | 0.0487 (4) | |
N1 | −0.0563 (6) | 0.4693 (11) | 0.6162 (5) | 0.055 (2) | |
C1 | 0.3671 (6) | −0.2184 (13) | 0.4545 (5) | 0.043 (2) | |
C2 | 0.4151 (6) | −0.2818 (16) | 0.5312 (5) | 0.055 (2) | |
H2 | 0.4433 | −0.4217 | 0.5367 | 0.066* | |
C3 | 0.4210 (6) | −0.1319 (16) | 0.6019 (5) | 0.055 (2) | |
H3 | 0.4562 | −0.1695 | 0.6552 | 0.066* | |
C4 | 0.3768 (5) | 0.0699 (13) | 0.5960 (5) | 0.0394 (19) | |
C5 | 0.3297 (6) | 0.1216 (13) | 0.5151 (5) | 0.046 (2) | |
H5 | 0.3014 | 0.2613 | 0.5089 | 0.055* | |
C6 | 0.3215 (6) | −0.0195 (14) | 0.4429 (5) | 0.050 (2) | |
H6 | 0.2871 | 0.0176 | 0.3892 | 0.061* | |
C7 | 0.3859 (6) | 0.2246 (15) | 0.6700 (5) | 0.050 (2) | |
H7 | 0.4442 | 0.2300 | 0.7017 | 0.060* | |
C8 | 0.3242 (6) | 0.3591 (14) | 0.6993 (5) | 0.047 (2) | |
H8 | 0.3483 | 0.4566 | 0.7442 | 0.056* | |
C9 | 0.2261 (6) | 0.3859 (12) | 0.6758 (4) | 0.042 (2) | |
C10 | 0.1699 (6) | 0.2157 (13) | 0.6391 (4) | 0.039 (2) | |
H10 | 0.1963 | 0.0776 | 0.6278 | 0.047* | |
C11 | 0.0804 (6) | 0.2435 (12) | 0.6198 (5) | 0.041 (2) | |
H11 | 0.0458 | 0.1253 | 0.5936 | 0.049* | |
C12 | 0.0344 (6) | 0.4455 (11) | 0.6371 (5) | 0.0369 (18) | |
C13 | 0.0914 (6) | 0.6088 (12) | 0.6775 (4) | 0.042 (2) | |
H13 | 0.0663 | 0.7459 | 0.6924 | 0.050* | |
C14 | 0.1825 (6) | 0.5720 (12) | 0.6956 (5) | 0.043 (2) | |
H14 | 0.2178 | 0.6859 | 0.7242 | 0.052* | |
C15 | −0.1121 (6) | 0.3046 (14) | 0.5665 (6) | 0.054 (2) | |
H15A | −0.0868 | 0.2745 | 0.5105 | 0.081* | |
H15B | −0.1742 | 0.3600 | 0.5547 | 0.081* | |
H15C | −0.1127 | 0.1692 | 0.6012 | 0.081* | |
C16 | −0.1007 (6) | 0.6780 (14) | 0.6312 (6) | 0.055 (2) | |
H16A | −0.0761 | 0.7393 | 0.6880 | 0.082* | |
H16B | −0.1661 | 0.6543 | 0.6319 | 0.082* | |
H16C | −0.0898 | 0.7805 | 0.5837 | 0.082* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0677 (7) | 0.0433 (5) | 0.0349 (4) | 0.0116 (4) | 0.0043 (3) | −0.0004 (4) |
N1 | 0.080 (7) | 0.033 (4) | 0.053 (4) | 0.003 (4) | 0.010 (4) | −0.008 (3) |
C1 | 0.068 (6) | 0.037 (5) | 0.025 (4) | 0.000 (4) | 0.010 (4) | 0.008 (3) |
C2 | 0.057 (6) | 0.069 (6) | 0.038 (5) | 0.022 (5) | 0.001 (4) | 0.001 (5) |
C3 | 0.047 (6) | 0.085 (7) | 0.032 (4) | 0.014 (5) | −0.001 (4) | 0.005 (5) |
C4 | 0.037 (5) | 0.051 (5) | 0.030 (4) | −0.010 (4) | 0.002 (3) | −0.001 (4) |
C5 | 0.061 (6) | 0.043 (5) | 0.036 (4) | 0.003 (4) | 0.014 (4) | 0.006 (4) |
C6 | 0.064 (6) | 0.062 (6) | 0.025 (4) | 0.019 (5) | 0.004 (4) | 0.015 (4) |
C7 | 0.058 (6) | 0.059 (6) | 0.031 (4) | −0.012 (5) | 0.000 (4) | 0.008 (4) |
C8 | 0.066 (7) | 0.052 (5) | 0.024 (4) | −0.011 (5) | 0.011 (4) | 0.001 (4) |
C9 | 0.075 (7) | 0.030 (5) | 0.020 (3) | −0.006 (4) | 0.007 (3) | 0.004 (3) |
C10 | 0.065 (6) | 0.036 (5) | 0.019 (3) | −0.008 (4) | 0.014 (3) | −0.007 (3) |
C11 | 0.068 (7) | 0.031 (4) | 0.026 (4) | −0.017 (4) | 0.012 (4) | 0.001 (3) |
C12 | 0.055 (6) | 0.026 (4) | 0.031 (4) | 0.004 (4) | 0.014 (3) | 0.003 (3) |
C13 | 0.082 (7) | 0.021 (4) | 0.024 (4) | −0.003 (4) | 0.007 (4) | −0.004 (3) |
C14 | 0.075 (7) | 0.030 (4) | 0.024 (4) | −0.011 (4) | 0.005 (4) | −0.004 (3) |
C15 | 0.068 (7) | 0.038 (5) | 0.055 (5) | −0.003 (4) | 0.007 (4) | 0.000 (4) |
C16 | 0.069 (7) | 0.045 (5) | 0.049 (5) | 0.006 (4) | 0.001 (4) | −0.009 (4) |
Br1—C1 | 1.927 (8) | C8—H8 | 0.9500 |
N1—C12 | 1.359 (11) | C9—C14 | 1.353 (11) |
N1—C16 | 1.460 (10) | C9—C10 | 1.412 (10) |
N1—C15 | 1.465 (11) | C10—C11 | 1.342 (11) |
C1—C2 | 1.364 (10) | C10—H10 | 0.9500 |
C1—C6 | 1.391 (11) | C11—C12 | 1.443 (10) |
C2—C3 | 1.408 (12) | C11—H11 | 0.9500 |
C2—H2 | 0.9500 | C12—C13 | 1.408 (11) |
C3—C4 | 1.392 (11) | C13—C14 | 1.371 (11) |
C3—H3 | 0.9500 | C13—H13 | 0.9500 |
C4—C5 | 1.393 (10) | C14—H14 | 0.9500 |
C4—C7 | 1.465 (11) | C15—H15A | 0.9800 |
C5—C6 | 1.392 (11) | C15—H15B | 0.9800 |
C5—H5 | 0.9500 | C15—H15C | 0.9800 |
C6—H6 | 0.9500 | C16—H16A | 0.9800 |
C7—C8 | 1.334 (12) | C16—H16B | 0.9800 |
C7—H7 | 0.9500 | C16—H16C | 0.9800 |
C8—C9 | 1.472 (12) | ||
C12—N1—C16 | 120.5 (7) | C10—C9—C8 | 123.1 (7) |
C12—N1—C15 | 123.1 (7) | C11—C10—C9 | 121.9 (8) |
C16—N1—C15 | 115.9 (7) | C11—C10—H10 | 119.1 |
C2—C1—C6 | 124.3 (8) | C9—C10—H10 | 119.1 |
C2—C1—Br1 | 117.8 (6) | C10—C11—C12 | 122.7 (7) |
C6—C1—Br1 | 117.9 (6) | C10—C11—H11 | 118.7 |
C1—C2—C3 | 117.4 (8) | C12—C11—H11 | 118.7 |
C1—C2—H2 | 121.3 | N1—C12—C13 | 124.4 (7) |
C3—C2—H2 | 121.3 | N1—C12—C11 | 121.4 (7) |
C4—C3—C2 | 121.9 (7) | C13—C12—C11 | 114.2 (8) |
C4—C3—H3 | 119.0 | C14—C13—C12 | 120.7 (7) |
C2—C3—H3 | 119.0 | C14—C13—H13 | 119.7 |
C3—C4—C5 | 116.8 (7) | C12—C13—H13 | 119.7 |
C3—C4—C7 | 120.7 (7) | C9—C14—C13 | 125.0 (7) |
C5—C4—C7 | 122.4 (8) | C9—C14—H14 | 117.5 |
C6—C5—C4 | 123.8 (8) | C13—C14—H14 | 117.5 |
C6—C5—H5 | 118.1 | N1—C15—H15A | 109.5 |
C4—C5—H5 | 118.1 | N1—C15—H15B | 109.5 |
C1—C6—C5 | 115.7 (7) | H15A—C15—H15B | 109.5 |
C1—C6—H6 | 122.2 | N1—C15—H15C | 109.5 |
C5—C6—H6 | 122.2 | H15A—C15—H15C | 109.5 |
C8—C7—C4 | 129.5 (8) | H15B—C15—H15C | 109.5 |
C8—C7—H7 | 115.2 | N1—C16—H16A | 109.5 |
C4—C7—H7 | 115.2 | N1—C16—H16B | 109.5 |
C7—C8—C9 | 132.6 (8) | H16A—C16—H16B | 109.5 |
C7—C8—H8 | 113.7 | N1—C16—H16C | 109.5 |
C9—C8—H8 | 113.7 | H16A—C16—H16C | 109.5 |
C14—C9—C10 | 115.4 (8) | H16B—C16—H16C | 109.5 |
C14—C9—C8 | 121.3 (7) | ||
C6—C1—C2—C3 | −2.3 (14) | C14—C9—C10—C11 | 4.5 (10) |
Br1—C1—C2—C3 | 177.7 (6) | C8—C9—C10—C11 | 178.7 (7) |
C1—C2—C3—C4 | 2.7 (13) | C9—C10—C11—C12 | −1.8 (10) |
C2—C3—C4—C5 | −2.9 (12) | C16—N1—C12—C13 | 3.1 (11) |
C2—C3—C4—C7 | −178.7 (8) | C15—N1—C12—C13 | 173.9 (7) |
C3—C4—C5—C6 | 2.8 (12) | C16—N1—C12—C11 | −177.6 (7) |
C7—C4—C5—C6 | 178.5 (8) | C15—N1—C12—C11 | −6.8 (11) |
C2—C1—C6—C5 | 2.1 (13) | C10—C11—C12—N1 | 179.5 (7) |
Br1—C1—C6—C5 | −177.8 (6) | C10—C11—C12—C13 | −1.1 (10) |
C4—C5—C6—C1 | −2.4 (12) | N1—C12—C13—C14 | −179.3 (7) |
C3—C4—C7—C8 | −142.8 (9) | C11—C12—C13—C14 | 1.3 (9) |
C5—C4—C7—C8 | 41.7 (13) | C10—C9—C14—C13 | −4.4 (10) |
C4—C7—C8—C9 | 7.1 (15) | C8—C9—C14—C13 | −178.8 (7) |
C7—C8—C9—C14 | −160.7 (9) | C12—C13—C14—C9 | 1.5 (11) |
C7—C8—C9—C10 | 25.4 (12) |
Experimental details
Crystal data | |
Chemical formula | C16H16BrN |
Mr | 302.21 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 123 |
a, b, c (Å) | 14.804 (2), 6.0962 (5), 15.2106 (10) |
β (°) | 95.331 (9) |
V (Å3) | 1366.8 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.99 |
Crystal size (mm) | 0.38 × 0.25 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.457, 0.749 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8606, 2986, 1533 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.075, 0.213, 0.99 |
No. of reflections | 2986 |
No. of parameters | 165 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.94, −0.54 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SAINT (Bruker, 2007, SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), PARST95 (Nardelli, 1995).
Acknowledgements
RMF is grateful to the Spanish Research Council (CSIC) for the use of a free-of-charge licence to the Cambridge Structural Database (Allen, 2002). RMF also thanks the Universidad del Valle, Colombia, for partial financial support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The present work is part of a structural study of molecular complexes based on the matrix of stilbene which can be used as non-linear optical material (He et al., 2008). Our research group has developed the study of other related systems of stilbene (Moreno-Fuquen et al., 2008; Moreno-Fuquen et al., 2009). Though the present molecular system is centrosymmetric, information about its crystal structure is very important to the study of the general behavior of stilbenes because crystallographic information of stilbene systems is still rather small. The main objective of the present work is to present the molecular and crystal structure of the 4-dimethylamino-4'-bromostilbene (DMBS) and to analyse the conformational structure of the system. A perspective view of the molecule of the title compound, showing the atomic numbering scheme, is given in Fig. 1. The benzene rings ot the title structure are inclined to each other showing a dihedral angle between their mean planes of 50.5 (3)°. The phenyl rings are twisted out of the ethylene bond plane, and are defined by the the torsion angles C5—C4—C7=C8 and C7=C8—C9—C10. The dimethylamino group forms a dihedral angle of 8.6 (7)° with respect to its phenyl ring. The title molecule shows a torsion angle C4 C7 C8 C9 of 7.1 (15)° indicating the existence of a great repulsion between the aromatic rings. These values allow to define its conformation structure as cis. The title system does not observe the formation of intermolecular hydrogen bonds.