organic papers
Acta Cryst.(2004). E60, o1211±o1212 DOI: 10.1107/S160053680401428X Cengiz Arõcõet al. C19H19NO2
o1211
Acta Crystallographica Section EStructure Reports
Online
ISSN 1600-5368
1-(3-Amino-1-benzofuran-2-yl)-2-mesityl-ethanone
Cengiz Arõcõ,a* DincËer UÈlkuÈ,a
Cumhur KõrõlmõsË,bMurat Kocab
and Misir Ahmedzadeb
aDepartment of Engineering Physics, Hacettepe University, Beytepe 06800, Ankara, Turkey, and bDepartment of Chemistry, Faculty of Arts and
Science, Fõrat University, 23169 Elazõg, Turkey
Correspondence e-mail: arici@hacettepe.edu.tr
Key indicators Single-crystal X-ray study
T= 293 K
Mean(C±C) = 0.005 AÊ
Rfactor = 0.054
wRfactor = 0.132
Data-to-parameter ratio = 11.9
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, C19H19NO2, features a benzofuran ring
system coplanar with an amino substituent and linked to a mesityl group by an acetyl bridge. In the crystal structure, symmetry-related molecules are linked by NÐH O inter-molecular hydrogen bonds involving one amino H atom and the O atom of the acetyl group to form in®nite chains. The other amino H atom is involved in an intramolecular hydrogen bond with the acetyl O atom.
Comment
Benzofuran derivatives possess antimicrobial, bacteriostatic, bactericidal, fungistatic and fungicidal activities (Hassaneenet al., 2002). Moreover, benzofurans are building blocks for optical brighteners and are applied, for example, in combin-ation with benzimidazoles as biphenyl end groups (Schmidt, 1999). Many of the natural benzofurans have physiological, pharmacological and toxic properties and, as a result, there is continuing interest in their chemical synthesis (Kappe et al., 1997).
The benzofuran ring system of the title compound, (2), is planar [with a maximum deviation from the plane of 0.101 (3) AÊ for C7] and the acetyl group is slightly twisted about the C1ÐC9 bond, as seen from the torsion angles O1Ð C1ÐC9ÐO2 [5.7 (3)] and C2ÐC1ÐC9ÐC10 [13.2 (3)].
Because of the amino group, the acetyl group is more twisted about the C1ÐC9 bond than in a similar compound (Arõcõet al., 2004). The benzofuran ring system is linked to the mesityl group by the acetyl group. The dihedral angle between the benzofuran ring system and the mesityl group is 79.91 (9).
The structure is stabilized by intramolecular and inter-molecular hydrogen-bonding interactions. In the crystal structure, molecules related by the 21rotation axis are linked
by NÐH O intermolecular hydrogen bonds involving an amino H atom and the O atom of the acetyl group to form in®nite chains along the b axis. The other amino H atom is involved in an intramolecular hydrogen bond with the acetyl O atom. Adjacent chains are interlinked through weak CÐ H interactions involving the furan ring.
Experimental
A mixture of 1-chloro-3-mesitylacetone, (1) (5 g, 23.73 mmol), 2-hydroxybenzaldehyde (2.85 g, 24 mmol) and K2CO3 (6.55 g,
47.46 mmol) in absolute acetone was re¯uxed for 8 h. After cooling, compound (2) (6.02 g, 89.3%) was ®ltered off, washed with water, dried and recrystallized from tetrahydrofuran.
Crystal data C19H19NO2
Mr= 293.35
Monoclinic,P21=c
a= 10.3779 (12) AÊ b= 10.3151 (11) AÊ c= 15.2789 (13) AÊ
= 105.116 (4)
V= 1579.0 (3) AÊ3
Z= 4
Dx= 1.234 Mg mÿ3
MoKradiation Cell parameters from 25
re¯ections
= 2.4±24.6
= 0.08 mmÿ1
T= 293 (2) K Prism, colourless 0.250.200.15 mm Data collection
Enraf±Nonius CAD-4 diffractometer
!/2scans
Absorption correction: scan (Fair, 1990)
Tmin= 0.981,Tmax= 0.988
2499 measured re¯ections 2370 independent re¯ections 1392 re¯ections withI> 2(I)
Rint= 0.046
max= 24.6
h=ÿ12!0 k=ÿ12!0 l=ÿ17!17 3 standard re¯ections
frequency: 120 min intensity decay: 0.7%
Re®nement Re®nement onF2
R[F2> 2(F2)] = 0.054
wR(F2) = 0.132
S= 1.01 2370 re¯ections 200 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0639P)2
+ 1.0373P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.24 e AÊÿ3
min=ÿ0.27 e AÊÿ3
Extinction correction:SHELXL97 Extinction coef®cient: 0.097 (19)
Table 1
Selected bond distances (AÊ).
C1ÐO1 1.408 (4)
C2ÐN1 1.346 (4) C4ÐO1 1.373 (4)
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N1ÐH1A O2 0.86 2.37 2.927 (4) 122 N1ÐH1B O2i 0.86 2.43 3.076 (4) 133
Symmetry code: (i) 1ÿx;yÿ1 2;12ÿz.
All H atoms were positioned geometrically (NÐH = 0.86 and CÐ H = 0.93±0.97 AÊ)and re®ned as riding, withUeq(H) = 1.2Ueq(C,N).
Data collection: CAD-4 EXPRESS (Enraf±Nonius, 1993); cell re®nement: CAD-4EXPRESS; program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON2000 (Spek, 2000); software used to prepare material for publication:
SHELXL97.
The authors acknowledge the purchase of the CAD-4 diffractometer under grant DPT/TBAG1 from the Scienti®c and Technical Research Council of Turkey.
References
Arõcõ, C., UÈlkuÈ, D., KõrõlmõsË, C., Koca, M. & Ahmedzade, M.Acta Cryst.E60, m941±m942.
Enraf±Nonius (1993).CAD-4EXPRESS. Version 1.1. Enraf±Nonius, Delft, The Netherlands.
Fair, C. K. (1990).MolEN.Enraf±Nonius, Delft, The Netherlands.
Hassaneen, H. M., Atta, S. M. S., Fawzy, N. M., Ahmed, F. A., Hegazi, A. G., Abdalla, F. A. & Abd El Rahman, A. H. (2002).Arch. Pharm. Med. Chem.
6, 251±261.
Kappe, C., Murphree, S. & Padwa, A. (1997).Tetrahedron,53, 14179±14233. Schmidt, E. (1999). InUllmann's Ecyclopedia, 6th ed. (electronic release);
Optical Brighteners. Weinheim: Wiley-VCH.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈttingen, Germany.
Spek, A. L. (2000).PLATON.University of Utrecht, The Netherlands.
Figure 1
A view of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small circles with arbitrary radii.
Figure 2
supporting information
sup-1 Acta Cryst. (2004). E60, o1211–o1212
supporting information
Acta Cryst. (2004). E60, o1211–o1212 [https://doi.org/10.1107/S160053680401428X]
1-(3-Amino-1-benzofuran-2-yl)-2-mesitylethanone
Cengiz Ar
ı
c
ı
, Din
ç
er
Ü
lk
ü
, Cumhur K
ı
r
ı
lm
ış
, Murat Koca and Misir Ahmedzade
(2)
Crystal data
C19H19NO2 Mr = 293.35 Monoclinic, P21/c Hall symbol: -P 2ybc a = 10.3779 (12) Å b = 10.3151 (11) Å c = 15.2789 (13) Å β = 105.116 (4)° V = 1579.0 (3) Å3 Z = 4
F(000) = 624 Dx = 1.234 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections θ = 2.4–24.6°
µ = 0.08 mm−1 T = 293 K Prism, colourless 0.25 × 0.20 × 0.15 mm
Data collection
CAD-4 EXPRESS (Enraf–Nonius, 1993) diffractometer
ω/2θ scans
Absorption correction: ψ scan
empirical (using intensity measurements) via ψ scans (Fair, 1990)
Tmin = 0.981, Tmax = 0.988 2499 measured reflections 2370 independent reflections
1392 reflections with I > 2σ(I) Rint = 0.046
θmax = 24.6° h = −12→0 k = −12→0 l = −17→17
3 standard reflections every 120 min intensity decay: 0.7%
Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.054 wR(F2) = 0.132 S = 1.01 2370 reflections 200 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.0639P)2 + 1.0373P] where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001 Δρmax = 0.24 e Å−3 Δρmin = −0.27 e Å−3
Special details
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)
x y z Uiso*/Ueq
O1 0.1455 (2) 0.3710 (2) 0.12700 (15) 0.0461 (7)
O2 0.4404 (2) 0.5653 (2) 0.16677 (17) 0.0538 (8)
N1 0.4633 (3) 0.3461 (3) 0.2915 (2) 0.0543 (9)
C1 0.2769 (3) 0.4131 (3) 0.1664 (2) 0.0412 (9)
C2 0.3389 (3) 0.3339 (3) 0.2372 (2) 0.0378 (9)
C3 0.2424 (3) 0.2361 (3) 0.2436 (2) 0.0379 (9)
C4 0.1275 (3) 0.2636 (3) 0.1756 (2) 0.0402 (9)
C5 0.0126 (4) 0.1923 (4) 0.1608 (3) 0.0466 (10)
C6 0.0141 (4) 0.0886 (4) 0.2179 (3) 0.0497 (10)
C7 0.1266 (4) 0.0577 (4) 0.2869 (2) 0.0490 (10)
C8 0.2416 (4) 0.1297 (3) 0.3002 (2) 0.0456 (10)
C9 0.3282 (4) 0.5208 (3) 0.1283 (2) 0.0411 (9)
C10 0.2502 (4) 0.5746 (3) 0.0383 (2) 0.0494 (10)
C11 0.2656 (3) 0.7194 (3) 0.0273 (2) 0.0393 (9)
C12 0.2019 (4) 0.8036 (4) 0.0740 (2) 0.0459 (10)
C13 0.2081 (4) 0.9362 (4) 0.0604 (3) 0.0521 (10)
C14 0.2745 (4) 0.9876 (4) 0.0015 (3) 0.0477 (10)
C15 0.3391 (4) 0.9035 (4) −0.0430 (2) 0.0483 (10)
C16 0.3365 (3) 0.7694 (3) −0.0314 (2) 0.0430 (9)
C17 0.1251 (5) 0.7534 (4) 0.1377 (3) 0.0819 (15)
C18 0.2747 (5) 1.1327 (4) −0.0158 (3) 0.0768 (14)
C19 0.4086 (4) 0.6836 (4) −0.0829 (3) 0.0724 (14)
H1A 0.5132 0.4092 0.2834 0.065*
H1B 0.4928 0.2909 0.3342 0.065*
H5 −0.0626 0.2128 0.1147 0.056*
H6 −0.0622 0.0379 0.2100 0.060*
H7 0.1239 −0.0125 0.3245 0.059*
H8 0.3172 0.1081 0.3458 0.055*
H10A 0.1564 0.5555 0.0306 0.059*
H10B 0.2783 0.5303 −0.0096 0.059*
H13 0.1661 0.9920 0.0920 0.062*
H15 0.3859 0.9373 −0.0821 0.058*
H17A 0.0885 0.8249 0.1634 0.123*
H17B 0.1838 0.7046 0.1853 0.123*
H17C 0.0541 0.6984 0.1051 0.123*
H18A 0.2245 1.1761 0.0202 0.115*
H18B 0.2348 1.1496 −0.0788 0.115*
H18C 0.3649 1.1642 0.0004 0.115*
supporting information
sup-3 Acta Cryst. (2004). E60, o1211–o1212
H19B 0.5017 0.7053 −0.0668 0.109*
H19C 0.3720 0.6963 −0.1468 0.109*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
O1 0.0419 (14) 0.0388 (15) 0.0495 (15) 0.0072 (12) −0.0025 (12) 0.0012 (12)
O2 0.0468 (15) 0.0419 (15) 0.0632 (17) 0.0037 (13) −0.0025 (13) −0.0028 (13)
N1 0.0460 (19) 0.051 (2) 0.056 (2) 0.0101 (16) −0.0047 (16) −0.0045 (16)
C1 0.036 (2) 0.033 (2) 0.049 (2) −0.0008 (18) 0.0019 (17) 0.0005 (17)
C2 0.037 (2) 0.033 (2) 0.041 (2) −0.0013 (17) 0.0060 (17) 0.0048 (17)
C3 0.038 (2) 0.034 (2) 0.040 (2) −0.0014 (17) 0.0081 (17) 0.0065 (17)
C4 0.043 (2) 0.032 (2) 0.044 (2) 0.0038 (17) 0.0084 (18) 0.0075 (18)
C5 0.039 (2) 0.047 (2) 0.048 (2) −0.0022 (19) 0.0027 (18) −0.0008 (19)
C6 0.049 (2) 0.045 (2) 0.057 (2) −0.005 (2) 0.018 (2) −0.005 (2)
C7 0.055 (2) 0.043 (2) 0.050 (2) 0.0050 (19) 0.015 (2) 0.000 (2)
C8 0.048 (2) 0.042 (2) 0.044 (2) 0.0063 (19) 0.0063 (17) 0.0043 (19)
C9 0.042 (2) 0.032 (2) 0.048 (2) −0.0032 (17) 0.0071 (18) 0.0034 (18)
C10 0.058 (2) 0.037 (2) 0.046 (2) 0.0024 (18) 0.0014 (19) −0.0028 (19)
C11 0.038 (2) 0.038 (2) 0.038 (2) 0.0012 (17) 0.0022 (17) 0.0002 (17)
C12 0.052 (2) 0.042 (2) 0.046 (2) 0.0060 (18) 0.0178 (19) 0.0027 (19)
C13 0.064 (3) 0.041 (2) 0.057 (2) 0.002 (2) 0.026 (2) 0.012 (2)
C14 0.053 (2) 0.034 (2) 0.055 (2) 0.0061 (19) 0.013 (2) 0.0025 (19)
C15 0.052 (2) 0.047 (2) 0.048 (2) 0.001 (2) 0.0163 (19) −0.0077 (19)
C16 0.039 (2) 0.043 (2) 0.045 (2) −0.0078 (18) 0.0081 (17) −0.0042 (18)
C17 0.111 (4) 0.065 (3) 0.088 (3) 0.013 (3) 0.058 (3) 0.013 (3)
C18 0.093 (4) 0.044 (3) 0.096 (4) 0.014 (2) 0.029 (3) −0.001 (2)
C19 0.075 (3) 0.063 (3) 0.090 (3) −0.025 (3) 0.040 (3) −0.013 (2)
Geometric parameters (Å, º)
C1—C2 1.374 (5) C11—C12 1.398 (5)
C1—O1 1.408 (4) C12—C13 1.388 (5)
C1—C9 1.421 (5) C12—C17 1.501 (5)
C2—N1 1.346 (4) C13—C14 1.374 (5)
C2—C3 1.442 (2) C13—H13 0.9300
C3—C4 1.391 (4) C14—C15 1.379 (5)
C3—C8 1.399 (5) C14—C18 1.520 (5)
C4—C5 1.370 (5) C15—C16 1.396 (5)
C4—O1 1.373 (4) C15—H15 0.9300
C5—C6 1.377 (5) C16—C19 1.507 (5)
C5—H5 0.9300 C17—H17A 0.9600
C6—C7 1.391 (5) C17—H17B 0.9600
C6—H6 0.9300 C17—H17C 0.9600
C7—C8 1.375 (5) C18—H18A 0.9600
C7—H7 0.9300 C18—H18B 0.9600
C8—H8 0.9300 C18—H18C 0.9600
C9—C10 1.508 (5) C19—H19B 0.9600
C10—C11 1.516 (5) C19—H19C 0.9600
C10—H10A 0.9700 N1—H1A 0.8600
C10—H10B 0.9700 N1—H1B 0.8600
C11—C16 1.396 (5)
C2—C1—O1 110.8 (3) C13—C12—C11 119.4 (4)
C2—C1—C9 129.7 (3) C13—C12—C17 119.4 (4)
O1—C1—C9 119.4 (3) C11—C12—C17 121.2 (3)
N1—C2—C1 127.3 (3) C14—C13—C12 121.9 (4)
N1—C2—C3 126.5 (3) C14—C13—H13 119.0
C1—C2—C3 106.2 (3) C12—C13—H13 119.0
C4—C3—C8 118.7 (3) C13—C14—C15 118.2 (4)
C4—C3—C2 106.3 (3) C13—C14—C18 121.1 (4)
C8—C3—C2 135.0 (3) C15—C14—C18 120.7 (4)
C5—C4—O1 125.4 (3) C14—C15—C16 122.2 (4)
C5—C4—C3 123.6 (3) C14—C15—H15 118.9
O1—C4—C3 111.0 (3) C16—C15—H15 118.9
C4—C5—C6 116.6 (3) C15—C16—C11 118.6 (3)
C4—C5—H5 121.7 C15—C16—C19 119.1 (4)
C6—C5—H5 121.7 C11—C16—C19 122.3 (3)
C5—C6—C7 121.8 (4) C12—C17—H17A 109.5
C5—C6—H6 119.1 C12—C17—H17B 109.5
C7—C6—H6 119.1 H17A—C17—H17B 109.5
C8—C7—C6 120.9 (4) C12—C17—H17C 109.5
C8—C7—H7 119.6 H17A—C17—H17C 109.5
C6—C7—H7 119.6 H17B—C17—H17C 109.5
C7—C8—C3 118.5 (3) C14—C18—H18A 109.5
C7—C8—H8 120.8 C14—C18—H18B 109.5
C3—C8—H8 120.8 H18A—C18—H18B 109.5
O2—C9—C1 119.9 (3) C14—C18—H18C 109.5
O2—C9—C10 120.5 (3) H18A—C18—H18C 109.5
C1—C9—C10 119.5 (3) H18B—C18—H18C 109.5
C9—C10—C11 114.6 (3) C16—C19—H19A 109.5
C9—C10—H10A 108.6 C16—C19—H19B 109.5
C11—C10—H10A 108.6 H19A—C19—H19B 109.5
C9—C10—H10B 108.6 C16—C19—H19C 109.5
C11—C10—H10B 108.6 H19A—C19—H19C 109.5
H10A—C10—H10B 107.6 H19B—C19—H19C 109.5
C16—C11—C12 119.7 (3) C4—O1—C1 105.6 (3)
C16—C11—C10 121.6 (3) C2—N1—H1A 120.0
C12—C11—C10 118.6 (3) C2—N1—H1B 120.0
O1—C1—C2—N1 −178.6 (3) C1—C9—C10—C11 148.2 (3)
C9—C1—C2—C3 −176.8 (3) C9—C10—C11—C12 −73.8 (4)
N1—C2—C3—C4 178.4 (3) C9—C10—C11—C16 109.3 (4)
C1—C2—C3—C8 −179.4 (4) C10—C11—C12—C13 −176.0 (3)
supporting information
sup-5 Acta Cryst. (2004). E60, o1211–o1212
C8—C3—C4—O1 179.7 (3) C17—C12—C13—C14 −178.6 (4)
O1—C4—C5—C6 −179.2 (3) C12—C13—C14—C18 177.1 (4)
C2—C3—C8—C7 178.4 (4) C18—C14—C15—C16 −177.4 (4)
C2—C1—C9—O2 −9.2 (6) C14—C15—C16—C19 179.5 (3)
O1—C1—C9—O2 174.3 (3) C10—C11—C16—C15 175.6 (3)
C2—C1—C9—C10 166.8 (4) C12—C11—C16—C19 179.3 (3)
O1—C1—C9—C10 −9.7 (5) C5—C4—O1—C1 179.2 (3)
O2—C9—C10—C11 −35.9 (5) C9—C1—O1—C4 177.4 (3)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N1—H1A···O2 0.8600 2.3700 2.927 (4) 122.00
N1—H1B···O2i 0.8600 2.4300 3.076 (4) 133.00
