PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. Oct 1, 2012; 68(Pt 10): o3028.
Published online Sep 29, 2012. doi:  10.1107/S1600536812037701
PMCID: PMC3470382
4-Meth­oxy-N-(4-meth­oxy-2-nitro­phen­yl)benzamide
Muhammad Arshad,a Sammer Yousuf,ab* Sumayya Saeed,b and Fatima Z. Bashaa
aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
bDepartment of Chemistry, University of Karachi, Karachi 75270, Pakistan
Correspondence e-mail: dr.sammer.yousuf/at/gmail.com
Additional corresponding author, e-mail: bashafz@gmail.com.
Received August 27, 2012; Accepted September 2, 2012.
In the title compound, C15H14N2O5, the central amide C—C(=O)—N—C unit forms dihedral angles of 28.17 (13) and 26.47 (13)° with the two benzene rings, whereas the two benzene rings are almost coplanar, making a dihedral angle of 4.52 (13)°. The two meth­oxy and the nitro substituents are almost coplanar with their attached benzene rings, with C—O—C—C torsion angles of −1.3 (4) and −4.6 (4)°, and an O—N—C—C torsion angle of 17.1 (3)°. In the crystal, mol­ecules are linked via C—H(...)O and N—H(...)O inter­actions, forming a tape running along the b axis.
Related literature  
For the crystal structures of related benzamide compounds, see: Sripet et al. (2012 [triangle]); Saeed et al. (2008 [triangle]); Saeed & Flörke (2009 [triangle]).
An external file that holds a picture, illustration, etc.
Object name is e-68-o3028-scheme1.jpg Object name is e-68-o3028-scheme1.jpg
Crystal data  
  • C15H14N2O5
  • M r = 302.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o3028-efi1.jpg
  • a = 9.7206 (12) Å
  • b = 4.9885 (6) Å
  • c = 28.725 (4) Å
  • β = 95.628 (2)°
  • V = 1386.2 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 273 K
  • 0.30 × 0.12 × 0.07 mm
Data collection  
  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.968, T max = 0.992
  • 7491 measured reflections
  • 2552 independent reflections
  • 1638 reflections with I > 2σ(I)
  • R int = 0.049
Refinement  
  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.155
  • S = 1.00
  • 2552 reflections
  • 205 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.19 e Å−3
Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 [triangle]) and PLATON (Spek, 2009 [triangle]).
Table 1
Table 1
Hydrogen-bond geometry (Å, °)
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812037701/is5189sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812037701/is5189Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536812037701/is5189Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
supplementary crystallographic information
Comment
The formation of amide functionality is a fundamental reaction and of great interest in organic chemistry. Due to a number of application in industrial and pharmaceutical areas as well as an important intermediate in synthetic chemistry, it remains a great challenge for the chemists to develop an efficient method for the synthesis of amides. The title compound was obtained during our attempt to synthesize libraries of benzamide derivatives under different conditions.
The molecule of title compound is not planner. The central amide unit (C6/C7/O2/N1/C8) forms dihedral angles of 28.17 (13) and 26.47 (13)°, respectively, with benzene C1–C6 and C8–C13 rings. The dihedral angle between the two C1–C6 and C8–C13 rings is 4.52 (13)°. The two methoxy and the nitro susbtituents lie nearly in plane of the corresponding aromatic rings with torsion angles C14—O3—C11—C12 of -4.6 (4)°, C15—O1—C3—C2 of -1.3 (4)°, O5—N2—C9—C10 of 17.1 (4)° and O4—N2—C9—C10 of -161.3 (3)°. The bond lengths and angles are similar to those found in the related benzamide derivatives (Sripet et al., 2012; Saeed et al., 2008; Saeed & Flörke, 2009). In the crystal, molecules are linked via intermolecular C—H···O and N—H···O (symmetry codes as in Table 2) interactions to form an infinite tape structure running along the b axis (Fig. 2).
Experimental
The title compound was synthesized by using the following procedure. To the stirring solution of 4-methoxy-2-nitroaniline (2.97 mmol) in 6.5 ml dichloromethane, p-methoxybenzoyl chloride (8.12 mmol) and triethylamine (0.5 ml) were added carefully at room temperature. The progress of reaction was checked by TLC and was completed in 12 h. Then the reaction mixture was diluted with water (25 ml) and acidified with 1.0 M HCl (50 ml). The organic compound was extracted with ethyl acetate (2×25 mL) and washed with brine (50 ml). The organic layer was dried (anhyd. MgSO4), filtered and concentrated on rotavapor. The crude mixture was purified by silica gel column chromatography by using ethyl acetate and hexane to get title compound with 77% yield. After column chromatography, the pure compound was left overnight. The crystals obtained were found suitable for single-crystal X-ray diffraction studies. All chemicals were purchased from Sigma-Aldrich and Alfa Aesar.
Refinement
The H atom on the nitrogen was located in a difference Fourier maps and refined freely [N—H = 0.80 (3) Å]. Other H atoms were positioned geometrically with 0.93 or 0.96 Å and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). A rotating group model was applied to the methyl groups.
Figures
Fig. 1.
Fig. 1.
The molecular structure of the title compound with displacement ellipsoids drawn at 30% probability level.
Fig. 2.
Fig. 2.
The crystal packing of the title compound. Hydrogen atoms are omitted for clearity. Dashed lines indicate the C—H···O and N—H···O hydrogen bonds.
Crystal data
C15H14N2O5F(000) = 632
Mr = 302.28Dx = 1.448 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2ynCell parameters from 1456 reflections
a = 9.7206 (12) Åθ = 2.3–28.0°
b = 4.9885 (6) ŵ = 0.11 mm1
c = 28.725 (4) ÅT = 273 K
β = 95.628 (2)°Plate, colorles
V = 1386.2 (3) Å30.30 × 0.12 × 0.07 mm
Z = 4
Data collection
Bruker SMART APEX CCD area-detector diffractometer2552 independent reflections
Radiation source: fine-focus sealed tube1638 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ω scanθmax = 25.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)h = −9→11
Tmin = 0.968, Tmax = 0.992k = −6→6
7491 measured reflectionsl = −34→34
Refinement
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155H atoms treated by a mixture of independent and constrained refinement
S = 1.00w = 1/[σ2(Fo2) + (0.0824P)2] where P = (Fo2 + 2Fc2)/3
2552 reflections(Δ/σ)max < 0.001
205 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = −0.19 e Å3
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.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
xyzUiso*/Ueq
O1−0.0633 (2)0.6081 (4)0.30064 (6)0.0569 (6)
O20.0516 (2)0.0858 (3)0.10748 (7)0.0621 (7)
O30.3257 (2)0.4247 (4)−0.08001 (6)0.0560 (6)
O40.3544 (2)0.8107 (5)0.11160 (7)0.0759 (8)
O50.4308 (2)1.0026 (4)0.05315 (7)0.0629 (7)
N10.1306 (2)0.5046 (4)0.09575 (8)0.0413 (6)
N20.3622 (2)0.8309 (4)0.06979 (8)0.0415 (6)
C10.1170 (3)0.6004 (5)0.19444 (9)0.0431 (7)
H1B0.18890.68720.18150.052*
C20.0863 (3)0.6723 (5)0.23865 (9)0.0465 (7)
H2A0.13830.80330.25540.056*
C3−0.0216 (3)0.5495 (5)0.25793 (9)0.0415 (7)
C4−0.0970 (3)0.3527 (6)0.23291 (9)0.0508 (8)
H4A−0.17090.27080.24560.061*
C5−0.0633 (3)0.2782 (5)0.18956 (9)0.0488 (8)
H5A−0.11300.14150.17360.059*
C60.0434 (3)0.4016 (4)0.16870 (8)0.0361 (6)
C70.0754 (3)0.3157 (4)0.12181 (8)0.0368 (6)
C80.1817 (3)0.4747 (4)0.05195 (8)0.0340 (6)
C90.2883 (3)0.6356 (4)0.03780 (8)0.0329 (6)
C100.3324 (3)0.6180 (5)−0.00614 (8)0.0381 (7)
H10A0.40170.7313−0.01460.046*
C110.2736 (3)0.4317 (5)−0.03782 (8)0.0386 (7)
C120.1694 (3)0.2690 (5)−0.02481 (9)0.0404 (7)
H12A0.12970.1416−0.04560.048*
C130.1236 (3)0.2943 (5)0.01899 (9)0.0413 (7)
H13A0.05110.18640.02660.050*
C140.2750 (3)0.2204 (6)−0.11201 (9)0.0567 (8)
H14A0.32270.2301−0.13970.085*
H14B0.17780.2458−0.12020.085*
H14C0.29050.0479−0.09760.085*
C150.0108 (4)0.8074 (6)0.32821 (9)0.0627 (9)
H15A−0.02760.82460.35760.094*
H15B0.00370.97580.31200.094*
H15C0.10620.75630.33360.094*
H1A0.138 (3)0.648 (6)0.1083 (9)0.059 (9)*
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
O10.0677 (16)0.0606 (12)0.0453 (11)−0.0009 (11)0.0196 (10)−0.0054 (10)
O20.1059 (19)0.0283 (9)0.0559 (12)−0.0171 (10)0.0273 (11)−0.0071 (9)
O30.0702 (16)0.0543 (11)0.0473 (11)−0.0215 (10)0.0250 (10)−0.0120 (9)
O40.085 (2)0.0929 (16)0.0514 (13)−0.0457 (14)0.0168 (11)−0.0209 (12)
O50.0706 (17)0.0463 (11)0.0716 (14)−0.0343 (11)0.0066 (11)0.0025 (10)
N10.0570 (18)0.0242 (11)0.0452 (13)−0.0096 (10)0.0184 (11)−0.0070 (10)
N20.0403 (16)0.0338 (11)0.0504 (14)−0.0078 (10)0.0051 (11)−0.0041 (11)
C10.0422 (19)0.0399 (14)0.0492 (16)−0.0091 (13)0.0147 (13)−0.0034 (13)
C20.056 (2)0.0392 (14)0.0449 (15)−0.0088 (13)0.0094 (14)−0.0082 (13)
C30.046 (2)0.0384 (14)0.0413 (15)0.0061 (13)0.0110 (13)0.0037 (12)
C40.049 (2)0.0525 (16)0.0533 (17)−0.0147 (14)0.0177 (14)0.0016 (14)
C50.057 (2)0.0408 (14)0.0493 (16)−0.0179 (14)0.0113 (14)−0.0033 (13)
C60.0405 (18)0.0255 (11)0.0432 (14)−0.0013 (11)0.0083 (12)0.0005 (11)
C70.0398 (18)0.0256 (12)0.0457 (14)−0.0004 (11)0.0085 (12)−0.0031 (11)
C80.0384 (18)0.0248 (11)0.0400 (14)−0.0019 (11)0.0110 (12)0.0002 (10)
C90.0321 (17)0.0226 (11)0.0438 (14)−0.0023 (10)0.0026 (12)−0.0019 (10)
C100.0377 (18)0.0307 (12)0.0477 (15)−0.0057 (12)0.0126 (12)0.0034 (11)
C110.0444 (19)0.0325 (12)0.0405 (14)0.0013 (12)0.0122 (12)−0.0002 (11)
C120.0469 (19)0.0299 (12)0.0454 (15)−0.0085 (12)0.0100 (13)−0.0080 (11)
C130.0434 (19)0.0334 (12)0.0488 (15)−0.0147 (12)0.0127 (13)−0.0068 (12)
C140.068 (2)0.0585 (18)0.0457 (16)−0.0103 (16)0.0147 (15)−0.0122 (14)
C150.097 (3)0.0487 (16)0.0445 (16)0.0080 (17)0.0159 (17)−0.0035 (14)
Geometric parameters (Å, º)
O1—C31.361 (3)C5—C61.391 (4)
O1—C151.422 (3)C5—H5A0.9300
O2—C71.232 (3)C6—C71.475 (3)
O3—C111.359 (3)C8—C131.386 (3)
O3—C141.427 (3)C8—C91.402 (3)
O4—N21.215 (3)C9—C101.375 (3)
O5—N21.212 (3)C10—C111.384 (3)
N1—C71.348 (3)C10—H10A0.9300
N1—C81.405 (3)C11—C121.378 (4)
N1—H1A0.80 (3)C12—C131.381 (3)
N2—C91.476 (3)C12—H12A0.9300
C1—C21.380 (3)C13—H13A0.9300
C1—C61.392 (3)C14—H14A0.9600
C1—H1B0.9300C14—H14B0.9600
C2—C31.377 (4)C14—H14C0.9600
C2—H2A0.9300C15—H15A0.9600
C3—C41.384 (4)C15—H15B0.9600
C4—C51.370 (4)C15—H15C0.9600
C4—H4A0.9300
C3—O1—C15118.2 (2)C13—C8—N1121.6 (2)
C11—O3—C14117.2 (2)C9—C8—N1122.3 (2)
C7—N1—C8128.2 (2)C10—C9—C8122.4 (2)
C7—N1—H1A113 (2)C10—C9—N2116.0 (2)
C8—N1—H1A118 (2)C8—C9—N2121.7 (2)
O5—N2—O4122.6 (2)C9—C10—C11120.1 (2)
O5—N2—C9118.2 (2)C9—C10—H10A120.0
O4—N2—C9119.2 (2)C11—C10—H10A120.0
C2—C1—C6121.8 (3)O3—C11—C12125.1 (2)
C2—C1—H1B119.1O3—C11—C10116.0 (2)
C6—C1—H1B119.1C12—C11—C10118.9 (2)
C3—C2—C1119.8 (2)C11—C12—C13120.3 (2)
C3—C2—H2A120.1C11—C12—H12A119.9
C1—C2—H2A120.1C13—C12—H12A119.9
O1—C3—C2125.0 (2)C12—C13—C8122.4 (2)
O1—C3—C4115.5 (3)C12—C13—H13A118.8
C2—C3—C4119.5 (2)C8—C13—H13A118.8
C5—C4—C3120.2 (3)O3—C14—H14A109.5
C5—C4—H4A119.9O3—C14—H14B109.5
C3—C4—H4A119.9H14A—C14—H14B109.5
C4—C5—C6121.8 (2)O3—C14—H14C109.5
C4—C5—H5A119.1H14A—C14—H14C109.5
C6—C5—H5A119.1H14B—C14—H14C109.5
C5—C6—C1116.9 (2)O1—C15—H15A109.5
C5—C6—C7119.8 (2)O1—C15—H15B109.5
C1—C6—C7123.3 (2)H15A—C15—H15B109.5
O2—C7—N1122.5 (2)O1—C15—H15C109.5
O2—C7—C6121.7 (2)H15A—C15—H15C109.5
N1—C7—C6115.8 (2)H15B—C15—H15C109.5
C13—C8—C9115.9 (2)
C6—C1—C2—C3−1.3 (4)C13—C8—C9—C100.4 (4)
C15—O1—C3—C2−1.3 (4)N1—C8—C9—C10−175.8 (2)
C15—O1—C3—C4179.6 (2)C13—C8—C9—N2−178.2 (2)
C1—C2—C3—O1−178.4 (2)N1—C8—C9—N25.6 (4)
C1—C2—C3—C40.7 (4)O5—N2—C9—C1017.1 (3)
O1—C3—C4—C5−179.8 (2)O4—N2—C9—C10−161.4 (2)
C2—C3—C4—C50.9 (4)O5—N2—C9—C8−164.2 (2)
C3—C4—C5—C6−2.1 (4)O4—N2—C9—C817.4 (4)
C4—C5—C6—C11.6 (4)C8—C9—C10—C11−1.7 (4)
C4—C5—C6—C7−179.6 (2)N2—C9—C10—C11177.0 (2)
C2—C1—C6—C50.2 (4)C14—O3—C11—C12−4.6 (4)
C2—C1—C6—C7−178.6 (2)C14—O3—C11—C10175.1 (2)
C8—N1—C7—O2−6.6 (4)C9—C10—C11—O3−178.6 (2)
C8—N1—C7—C6174.1 (2)C9—C10—C11—C121.1 (4)
C5—C6—C7—O2−27.8 (4)O3—C11—C12—C13−179.6 (2)
C1—C6—C7—O2150.9 (3)C10—C11—C12—C130.7 (4)
C5—C6—C7—N1151.5 (3)C11—C12—C13—C8−2.1 (4)
C1—C6—C7—N1−29.7 (4)C9—C8—C13—C121.5 (4)
C7—N1—C8—C1333.7 (4)N1—C8—C13—C12177.7 (2)
C7—N1—C8—C9−150.3 (3)
Hydrogen-bond geometry (Å, º)
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.80 (3)2.34 (3)3.027 (3)145 (3)
C10—H10A···O5ii0.932.453.364 (3)168
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+2, −z.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS5189).
References
  • Bruker (2000). SADABS, SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Nardelli, M. (1995). J. Appl. Cryst. 28, 659.
  • Saeed, A. & Flörke, U. (2009). Acta Cryst. E65, o1948. [PMC free article] [PubMed]
  • Saeed, A., Khera, R. A., Batool, M., Shaheen, U. & Flörke, U. (2008). Acta Cryst. E64, o1625. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Sripet, W., Chantrapromma, S., Ruanwas, P. & Fun, H.-K. (2012). Acta Cryst. E68, o1234. [PMC free article] [PubMed]
Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of
International Union of Crystallography