organic papers
Acta Cryst.(2004). E60, o2179±o2180 doi: 10.1107/S1600536804027412 Brian McBurneyet al. C8H9NO3
o2179
Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
1-Ethoxy-4-nitrobenzene
Brian McBurney,aPaul C. D. Foss,aElizabeth M. Reed,a Timothy D. Shine,aNeil M. Glagovich,aBarry L. Westcott,a Guy Crundwell,a* Matthias Zellerband Allen D. Hunterb
aDepartment of Chemistry, Central Connecticut
State University, New Britain, CT 06053, USA, andbDepartment of Chemistry, Youngstown
State University, One University Plaza, Youngs-town, Ohio 44555-3663, USA
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 100 K
Mean(C±C) = 0.002 AÊ
Rfactor = 0.048
wRfactor = 0.129
Data-to-parameter ratio = 14.2
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, C8H9NO3, was synthesized from
4-nitrophenol and ethyl iodide via the Williamson ether
synthesis. The crystal structure has been determined at 100 K.
Comment
1-Ethoxy-4-nitrobenzene, (I) (Fig. 1), also known asp -nitro-phenetole, was synthesized by undergraduate chemistry students as part of an undergraduate laboratory course. The students were preparing a variety of ethers in an effort to design a laboratory that could be incorporated into the undergraduate organic chemistry curriculum. Of the ethers prepared, 1-ethoxy-4-nitrobenzene required the shortest reaction time, gave the best yield, and was the least prob-lematic in terms of isolation. In addition, upon standing, a solution of (I) in ethanol produced very large and well de®ned crystals. Because the crystal structure of this ether has not been previously reported, it was decided that it would be an interesting extension of the laboratory experience to have the students in the class solve the structure from the X-ray diffraction data.
Experimental
To a 100 ml round-bottomed ¯ask equipped with a re¯ux condenser were added 15 ml of an 8% (w/w) sodium hydroxide solution,
p-nitrophenol (2.78 g, 19 mmol), ethyl iodide (3.2 g, 21 mmol) and acetone (25 ml). The resulting mixture was heated under re¯ux for 90 min. After this time, the resulting yellow solution was poured over 75 g of ice, and stirred until the ice melted. The crude yellow solid was collected by vacuum ®ltration and recrystallized from 95% ethanol to yieldp-nitrophenetole (yield: 2.64 g, 83%; m.p. 330.2 K). The NMR data agree with the published literature (Heathcock, 1962). IR (CHCl3): 3115, 3098, 2987, 1609, 1597, 1497, 1474, 1342, 1329, 1302,
1261, 1176, 1090, 1041, 920, 860, 851, 751, 655 cmÿ1; 1H NMR
(300 MHz, CDCl3):8.204 (d, 2H,J= 10.5 Hz), 6.944 (d, 2H,J=
10.5 Hz), 4.130 (q, 2H,J= 7.0 Hz), 1.465 (t, 3H,J= 7.0 Hz);13C NMR
Received 18 October 2004 Accepted 27 October 2004 Online 6 November 2004
Figure 1
(300 MHz, CDCl3):164.19, 141.39, 125.89, 114.48, 64.53, 14.56; MS
(calculated for C8H9NO3): M+: 167, measured: 167. Crystal data
C8H9NO3 Mr= 167.16 Monoclinic,P21=c a= 7.2796 (5) AÊ b= 11.7664 (8) AÊ c= 9.4285 (6) AÊ
= 104.957 (1) V= 780.23 (9) AÊ3 Z= 4
Dx= 1.423 Mg mÿ3 MoKradiation Cell parameters from 6367
re¯ections
= 2.2±28.3
= 0.11 mmÿ1 T= 100 (2) K Block, colorless 0.450.450.30 mm
Data collection
Bruker SMART APEX diffractometer
!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) Tmin= 0.948,Tmax= 0.969
8103 measured re¯ections
1936 independent re¯ections 1894 re¯ections withI> 2(I) Rint= 0.021
max= 28.3 h=ÿ9!9 k=ÿ15!15 l=ÿ12!12
Refinement
Re®nement onF2 R[F2> 2(F2)] = 0.048 wR(F2) = 0.129 S= 1.22 1936 re¯ections 136 parameters
All H-atom parameters re®ned
w= 1/[2(F
o2) + (0.0575P)2 + 0.3353P]
whereP= (Fo2+ 2Fc2)/3 (/)max= 0.020
max= 0.37 e AÊÿ3
min=ÿ0.23 e AÊÿ3
Positional and isotropic displacement parameters for all H atoms were allowed to re®ne after their location in a difference map.
Data collection: SMART (Bruker, 1997±1999); cell re®nement:
SAINT-Plus (Bruker, 1997±1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication:SHELXL97.
MZ and JU were supported by NSF grant 0111511, and the diffractometer was funded by NSF grant 0087210, by Ohio Board of Regents grant CAP-491, and by YSU.
References
Bruker (1997±1999).SMARTandSAINT-Plus.Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1997).J. Appl. Cryst.30, 565. Heathcock, H. (1962).Can. J. Chem.40, 1865±1865.
Sheldrick, G. M. (2003).SADABS.Version 2.10. University of GoÈttingen, Germany.
supporting information
sup-1
Acta Cryst. (2004). E60, o2179–o2180
supporting information
Acta Cryst. (2004). E60, o2179–o2180 [https://doi.org/10.1107/S1600536804027412]
1-Ethoxy-4-nitrobenzene
Brian McBurney, Paul C. D. Foss, Elizabeth M. Reed, Timothy D. Shine, Neil M. Glagovich,
Barry L. Westcott, Guy Crundwell, Matthias Zeller and Allen D. Hunter
1-ethoxy-4-nitrobenzene
Crystal data C8H9NO3 Mr = 167.16
Monoclinic, P21/c
Hall symbol: -P 2ybc a = 7.2796 (5) Å b = 11.7664 (8) Å c = 9.4285 (6) Å β = 104.957 (1)° V = 780.23 (9) Å3 Z = 4
F(000) = 352 Dx = 1.423 Mg m−3
Melting point: 330.2 K
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 6367 reflections θ = 2.2–28.3°
µ = 0.11 mm−1 T = 100 K Block, colorless 0.45 × 0.45 × 0.3 mm
Data collection Bruker SMART APEX
diffractometer
Radiation source: sealed tube Graphite monochromator ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) Tmin = 0.948, Tmax = 0.969
8103 measured reflections 1936 independent reflections 1894 reflections with I > 2σ(I) Rint = 0.021
θmax = 28.3°, θmin = 2.8° h = −9→9
k = −15→15 l = −12→12
Refinement Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.048 wR(F2) = 0.129 S = 1.22 1936 reflections 136 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
All H-atom parameters refined w = 1/[σ2(F
o2) + (0.0575P)2 + 0.3353P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.020
Δρmax = 0.37 e Å−3
Special details
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. H atoms were allowed to refine isotropically.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
O1 0.32511 (17) 0.68300 (9) 0.08392 (13) 0.0300 (3)
N1 0.23992 (16) 0.74291 (10) −0.01917 (13) 0.0200 (3)
C1 0.25281 (17) 0.86572 (11) −0.00128 (14) 0.0171 (3)
O2 0.14383 (16) 0.70363 (9) −0.13557 (12) 0.0290 (3)
C2 0.36067 (18) 0.91110 (11) 0.13039 (14) 0.0178 (3)
H2A 0.422 (2) 0.8638 (16) 0.207 (2) 0.021*
O3 0.30202 (14) 1.21136 (8) 0.05688 (11) 0.0206 (2)
C3 0.37343 (18) 1.02736 (11) 0.14606 (14) 0.0178 (3)
H3A 0.448 (2) 1.0590 (15) 0.236 (2) 0.021*
C4 0.27830 (18) 1.09830 (11) 0.03104 (14) 0.0172 (3)
C5 0.16852 (19) 1.05195 (11) −0.10042 (15) 0.0187 (3)
H5A 0.102 (2) 1.0991 (16) −0.180 (2) 0.022*
C6 0.15703 (19) 0.93450 (11) −0.11626 (15) 0.0187 (3)
H6A 0.085 (3) 0.9047 (16) −0.206 (2) 0.022*
C7 0.2128 (2) 1.28831 (11) −0.06000 (15) 0.0202 (3)
H7A 0.077 (3) 1.2750 (16) −0.088 (2) 0.024*
H7B 0.263 (2) 1.2760 (15) −0.144 (2) 0.024*
C8 0.2557 (2) 1.40737 (12) −0.00176 (17) 0.0253 (3)
H8A 0.193 (3) 1.463 (2) −0.079 (2) 0.038*
H8B 0.391 (3) 1.4193 (18) 0.032 (2) 0.038*
H8C 0.202 (3) 1.4192 (18) 0.082 (2) 0.038*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3
Acta Cryst. (2004). E60, o2179–o2180
C7 0.0248 (7) 0.0156 (6) 0.0194 (6) 0.0012 (5) 0.0043 (5) 0.0024 (5) C8 0.0351 (8) 0.0161 (6) 0.0246 (7) 0.0007 (5) 0.0077 (6) 0.0005 (5)
Geometric parameters (Å, º)
O1—N1 1.2309 (16) C4—C5 1.4004 (18)
N1—O2 1.2292 (15) C5—C6 1.3901 (19)
N1—C1 1.4551 (17) C5—H5A 0.956 (18)
C1—C6 1.3879 (18) C6—H6A 0.942 (19)
C1—C2 1.3928 (18) C7—C8 1.508 (2)
C2—C3 1.3764 (18) C7—H7A 0.966 (18)
C2—H2A 0.929 (19) C7—H7B 0.961 (18)
O3—C4 1.3554 (16) C8—H8A 1.00 (2)
O3—C7 1.4446 (16) C8—H8B 0.97 (2)
C3—C4 1.4018 (18) C8—H8C 0.97 (2)
C3—H3A 0.955 (18)
O2—N1—O1 122.98 (12) C6—C5—H5A 119.3 (11)
O2—N1—C1 118.79 (11) C4—C5—H5A 121.6 (11)
O1—N1—C1 118.22 (11) C1—C6—C5 119.45 (12)
C6—C1—C2 121.78 (12) C1—C6—H6A 122.4 (11)
C6—C1—N1 118.96 (11) C5—C6—H6A 118.1 (11)
C2—C1—N1 119.26 (11) O3—C7—C8 107.12 (11)
C3—C2—C1 118.92 (12) O3—C7—H7A 109.5 (11)
C3—C2—H2A 120.5 (11) C8—C7—H7A 110.6 (11)
C1—C2—H2A 120.6 (11) O3—C7—H7B 109.9 (11)
C4—O3—C7 117.81 (10) C8—C7—H7B 110.6 (11)
C2—C3—C4 120.18 (12) H7A—C7—H7B 109.2 (15)
C2—C3—H3A 119.3 (11) C7—C8—H8A 109.1 (13)
C4—C3—H3A 120.5 (11) C7—C8—H8B 110.7 (13)
O3—C4—C5 123.95 (12) H8A—C8—H8B 112.7 (17)
O3—C4—C3 115.52 (11) C7—C8—H8C 109.8 (12)
C5—C4—C3 120.52 (12) H8A—C8—H8C 107.1 (17)
C6—C5—C4 119.15 (12) H8B—C8—H8C 107.4 (18)
O2—N1—C1—C6 −0.27 (18) C2—C3—C4—O3 −179.19 (11)
O1—N1—C1—C6 −179.76 (12) C2—C3—C4—C5 0.4 (2)
O2—N1—C1—C2 179.74 (12) O3—C4—C5—C6 178.71 (12)
O1—N1—C1—C2 0.25 (18) C3—C4—C5—C6 −0.8 (2)
C6—C1—C2—C3 −0.50 (19) C2—C1—C6—C5 0.1 (2)
N1—C1—C2—C3 179.49 (11) N1—C1—C6—C5 −179.93 (12)
C1—C2—C3—C4 0.27 (19) C4—C5—C6—C1 0.6 (2)
C7—O3—C4—C5 −1.79 (19) C4—O3—C7—C8 178.26 (11)
