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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1470.
Published online 2009 June 6. doi:  10.1107/S1600536809020509
PMCID: PMC2969324

N-(3-Bromo­phen­yl)-3,4,5-trimethoxy­benzamide

Abstract

In the title compound, C16H16BrNO4, the dihedral between the planes of the aromatic rings is 7.74 (18)°. The amide group is tilted with respect to the bromo- and meth­oxy-substituted aromatic rings by 36.3 (8) and 35.2 (8)°, respectively. The meta-meth­oxy groups are essentially in-plane with the aromatic ring [dihedral angles CH3—O—C—C = −4.6 (4) and −2.5 (4)°]. The para-meth­oxy group is markedly displaced from the ring plane [dihedral angle CH3—O—C—C = −72.5 (4)°]. The crystal packing is stabilized by N—H(...)O hydrogen bonds linking the mol­ecules into chains running along the b axis.

Related literature

For related structures and general background, see: Saeed et al. (2009 [triangle]). For conformations of aromatic meth­oxy groups, see: Vande Velde et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1470-scheme1.jpg

Experimental

Crystal data

  • C16H16BrNO4
  • M r = 366.21
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1470-efi1.jpg
  • a = 13.3085 (8) Å
  • b = 4.9953 (3) Å
  • c = 23.4061 (12) Å
  • V = 1556.04 (15) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.66 mm−1
  • T = 173 K
  • 0.37 × 0.34 × 0.19 mm

Data collection

  • Stoe IPDS II two-circle diffractometer
  • Absorption correction: multi-scan [MULABS (Spek, 2009 [triangle]; Blessing, 1995 [triangle])] T min = 0.418, T max = 0.600
  • 11994 measured reflections
  • 3028 independent reflections
  • 2748 reflections with I > 2σ(I)
  • R int = 0.056

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.076
  • S = 0.99
  • 3028 reflections
  • 207 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.39 e Å−3
  • Absolute structure: Flack (1983 [triangle]), with 1405 Friedel pairs
  • Flack parameter: 0.001 (8)

Data collection: X-AREA (Stoe & Cie, 2001 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809020509/zl2213sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809020509/zl2213Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

AI gratefully acknowledges a research scholarship from the HEC, Islamabad, Pakistan, under the HEC Indigenous PhD Scholarship 5000 Scheme.

supplementary crystallographic information

Comment

The background to this study has been described in an earlier paper on N-(2-chlorophenyl)-4-chlorobenzamide (Saeed et al., 2009). As part of our work on the structure of benzanilides and related compounds, we report here the structure of the title compound, Fig. 1.

In the title compound, C16H16BrNO4, the dihedral angle between the aromatic rings is 7.74 (18)°. The amide moiety is tilted against the bromo and methoxy substituted aromatic rings by 36.3 (8)° and 35.2 (8)°, respectively. The meta methoxy groups are essentially in plane with the aromatic ring [dihedral angles CH3—O—C—C = -4.6 (4)° and -2.5 (4)°], the methoxy group in para position is markedly displaced from the ring plane [dihedral angle CH3—O—C—C = -72.5 (4)°]. This can be attributed to a combination of resonance effects, which lead for aromatic methoxy groups to being coplanar with an aromatic ring, and steric interactions, which prohibit a coplanar arrangement when more than two methoxy groups are present per benzene moiety (Vande Velde et al., 2006). The crystal packing is stabilized by N—H···O hydrogen bonds linking the molecules to chains running along the b axis (Fig. 2).

Experimental

3,4,5-Trimethoxybenzoyl chloride (5.4 mmol) in CHCl3 was treated with 3-bromoaniline (21.6 mmol) under a nitrogen atmosphere at reflux for 3 h. Upon cooling, the reaction mixture was diluted with CHCl3 and washed consecutively with aq 1 M HCl and saturated aq NaHCO3. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. Crystallization of the residue in CHCl3 afforded the title compound (81%) as colourless needles. Anal. calcd. for C16H16BrNO4: C, 52.48; H, 4.40; N, 3.82%; found: C, 52.51; H, 4.36; N, 3.87

Refinement

H atoms were located in a difference map but those bonded to C were geometrically positioned and refined using a riding model with fixed individual displacement parameters [U(Hiso) = 1.2Ueq(C) or U(Hiso) = 1.5Ueq(Cmethyl)] using a riding model with Caromatic—H = 0.95 Å or Cmethyl—H = 0.98 Å. The H atom bonded to N was freely refined.

Figures

Fig. 1.
The title compound with the atom numbering scheme; displacement ellipsoids are at the 50% probability level; H atoms are drawn as small spheres of arbitrary radii.
Fig. 2.
Partial packing diagram of the title compound. Hydrogen bonds are drawn as dashed lines.

Crystal data

C16H16BrNO4F(000) = 744
Mr = 366.21Dx = 1.563 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 11796 reflections
a = 13.3085 (8) Åθ = 3.5–26.7°
b = 4.9953 (3) ŵ = 2.66 mm1
c = 23.4061 (12) ÅT = 173 K
V = 1556.04 (15) Å3Plate, colourless
Z = 40.37 × 0.34 × 0.19 mm

Data collection

Stoe IPDS II two-circle diffractometer3028 independent reflections
Radiation source: fine-focus sealed tube2748 reflections with I > 2σ(I)
graphiteRint = 0.056
ω scansθmax = 26.3°, θmin = 3.5°
Absorption correction: multi-scan [MULABS (Spek, 2009; Blessing, 1995)]h = −16→16
Tmin = 0.418, Tmax = 0.600k = −6→6
11994 measured reflectionsl = −29→26

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.033w = 1/[σ2(Fo2) + (0.0493P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.076(Δ/σ)max < 0.001
S = 0.99Δρmax = 0.46 e Å3
3028 reflectionsΔρmin = −0.39 e Å3
207 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0168 (10)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with 1405 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.001 (8)

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
Br10.19897 (2)0.79946 (7)0.12371 (2)0.04356 (13)
N10.52764 (18)0.5080 (5)0.23414 (11)0.0203 (5)
H10.546 (3)0.351 (8)0.2441 (17)0.023 (9)*
O10.51118 (18)0.9515 (4)0.25246 (10)0.0285 (5)
O20.62891 (16)0.9862 (4)0.46087 (9)0.0276 (4)
O30.78413 (15)0.6364 (4)0.46308 (10)0.0259 (4)
O40.82971 (16)0.3369 (4)0.37342 (10)0.0276 (5)
C10.5457 (2)0.7303 (5)0.26493 (13)0.0204 (6)
C110.4666 (2)0.4924 (5)0.18432 (13)0.0220 (6)
C120.3799 (2)0.6447 (6)0.17818 (13)0.0246 (6)
H120.36130.77240.20630.030*
C130.3216 (2)0.6057 (6)0.13014 (16)0.0279 (6)
C140.3467 (3)0.4244 (7)0.08727 (14)0.0334 (7)
H140.30600.40430.05420.040*
C150.4334 (3)0.2740 (7)0.09471 (15)0.0332 (7)
H150.45200.14660.06650.040*
C160.4931 (3)0.3066 (6)0.14241 (13)0.0270 (6)
H160.55230.20220.14670.032*
C210.6099 (2)0.6961 (5)0.31655 (12)0.0201 (5)
C220.5883 (2)0.8619 (5)0.36327 (13)0.0220 (6)
H220.53430.98590.36140.026*
C230.6460 (2)0.8435 (5)0.41199 (12)0.0206 (6)
C240.7280 (2)0.6655 (5)0.41433 (13)0.0210 (6)
C250.7487 (2)0.5016 (5)0.36721 (13)0.0201 (5)
C260.6890 (2)0.5141 (5)0.31853 (13)0.0213 (6)
H260.70210.39970.28700.026*
C270.5500 (2)1.1804 (6)0.45934 (14)0.0279 (6)
H27A0.56101.30330.42730.042*
H27B0.54951.28170.49520.042*
H27C0.48531.08950.45450.042*
C280.8483 (3)0.8582 (7)0.47549 (15)0.0337 (7)
H28A0.90010.87270.44590.051*
H28B0.88050.83080.51270.051*
H28C0.80861.02320.47640.051*
C290.8502 (2)0.1607 (6)0.32691 (15)0.0287 (7)
H29A0.79100.04960.31940.043*
H29B0.90740.04560.33660.043*
H29C0.86640.26590.29280.043*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.02770 (15)0.0536 (2)0.0494 (2)0.00300 (13)−0.0092 (2)0.0107 (3)
N10.0287 (12)0.0138 (10)0.0184 (12)−0.0002 (9)−0.0028 (10)−0.0013 (9)
O10.0429 (12)0.0152 (9)0.0273 (11)0.0026 (8)−0.0104 (10)−0.0011 (8)
O20.0303 (11)0.0332 (10)0.0192 (10)0.0084 (8)−0.0025 (9)−0.0069 (9)
O30.0274 (10)0.0289 (10)0.0214 (11)−0.0008 (8)−0.0053 (8)0.0023 (8)
O40.0232 (10)0.0286 (11)0.0311 (12)0.0097 (8)−0.0021 (9)−0.0039 (9)
C10.0237 (13)0.0175 (12)0.0199 (14)−0.0026 (9)0.0012 (11)0.0009 (10)
C110.0280 (14)0.0206 (11)0.0176 (14)−0.0031 (11)0.0002 (11)0.0026 (11)
C120.0277 (15)0.0248 (13)0.0212 (14)−0.0013 (11)−0.0001 (12)0.0019 (11)
C130.0250 (12)0.0337 (13)0.0251 (18)−0.0052 (10)0.0008 (13)0.0053 (14)
C140.0352 (17)0.0428 (17)0.0223 (16)−0.0146 (14)−0.0052 (13)0.0034 (14)
C150.0402 (19)0.0357 (17)0.0235 (17)−0.0072 (14)0.0011 (14)−0.0058 (13)
C160.0326 (16)0.0253 (14)0.0232 (16)−0.0008 (12)0.0003 (12)−0.0039 (11)
C210.0225 (14)0.0169 (11)0.0208 (14)−0.0018 (10)−0.0025 (10)0.0014 (11)
C220.0244 (14)0.0184 (12)0.0232 (15)0.0018 (10)0.0007 (12)−0.0005 (10)
C230.0242 (14)0.0197 (13)0.0178 (14)−0.0015 (10)0.0040 (11)−0.0035 (11)
C240.0215 (13)0.0229 (13)0.0186 (14)−0.0018 (10)−0.0016 (11)0.0009 (11)
C250.0181 (12)0.0185 (13)0.0238 (15)−0.0001 (10)0.0005 (11)0.0021 (10)
C260.0243 (14)0.0191 (12)0.0205 (14)−0.0010 (10)0.0029 (11)−0.0019 (10)
C270.0324 (16)0.0244 (14)0.0269 (16)0.0064 (12)0.0015 (13)−0.0055 (12)
C280.0318 (17)0.0352 (17)0.0341 (19)−0.0032 (14)−0.0116 (14)−0.0036 (14)
C290.0296 (16)0.0257 (15)0.0308 (17)0.0070 (12)0.0062 (13)−0.0021 (13)

Geometric parameters (Å, °)

Br1—C131.903 (3)C15—H150.9500
N1—C11.346 (4)C16—H160.9500
N1—C111.423 (4)C21—C261.392 (4)
N1—H10.85 (4)C21—C221.401 (4)
O1—C11.232 (3)C22—C231.378 (4)
O2—C231.367 (3)C22—H220.9500
O2—C271.431 (3)C23—C241.409 (4)
O3—C241.371 (4)C24—C251.401 (4)
O3—C281.429 (4)C25—C261.391 (4)
O4—C251.363 (3)C26—H260.9500
O4—C291.426 (4)C27—H27A0.9800
C1—C211.490 (4)C27—H27B0.9800
C11—C121.389 (4)C27—H27C0.9800
C11—C161.396 (4)C28—H28A0.9800
C12—C131.380 (5)C28—H28B0.9800
C12—H120.9500C28—H28C0.9800
C13—C141.393 (5)C29—H29A0.9800
C14—C151.388 (5)C29—H29B0.9800
C14—H140.9500C29—H29C0.9800
C15—C161.379 (4)
C1—N1—C11125.9 (2)C21—C22—H22120.3
C1—N1—H1124 (2)O2—C23—C22124.4 (3)
C11—N1—H1110 (2)O2—C23—C24115.2 (2)
C23—O2—C27117.1 (2)C22—C23—C24120.4 (3)
C24—O3—C28114.4 (2)O3—C24—C25119.1 (3)
C25—O4—C29116.3 (2)O3—C24—C23121.4 (2)
O1—C1—N1123.2 (3)C25—C24—C23119.4 (3)
O1—C1—C21120.6 (2)O4—C25—C26124.5 (3)
N1—C1—C21116.2 (2)O4—C25—C24115.1 (3)
C12—C11—C16120.1 (3)C26—C25—C24120.4 (2)
C12—C11—N1121.9 (3)C25—C26—C21119.3 (3)
C16—C11—N1117.9 (3)C25—C26—H26120.4
C13—C12—C11118.3 (3)C21—C26—H26120.4
C13—C12—H12120.8O2—C27—H27A109.5
C11—C12—H12120.8O2—C27—H27B109.5
C12—C13—C14122.9 (3)H27A—C27—H27B109.5
C12—C13—Br1118.4 (3)O2—C27—H27C109.5
C14—C13—Br1118.7 (2)H27A—C27—H27C109.5
C15—C14—C13117.5 (3)H27B—C27—H27C109.5
C15—C14—H14121.3O3—C28—H28A109.5
C13—C14—H14121.3O3—C28—H28B109.5
C16—C15—C14121.1 (3)H28A—C28—H28B109.5
C16—C15—H15119.5O3—C28—H28C109.5
C14—C15—H15119.5H28A—C28—H28C109.5
C15—C16—C11120.1 (3)H28B—C28—H28C109.5
C15—C16—H16119.9O4—C29—H29A109.5
C11—C16—H16119.9O4—C29—H29B109.5
C26—C21—C22121.0 (3)H29A—C29—H29B109.5
C26—C21—C1122.4 (2)O4—C29—H29C109.5
C22—C21—C1116.6 (2)H29A—C29—H29C109.5
C23—C22—C21119.5 (3)H29B—C29—H29C109.5
C23—C22—H22120.3
C11—N1—C1—O1−0.9 (5)C27—O2—C23—C22−4.6 (4)
C11—N1—C1—C21178.3 (3)C27—O2—C23—C24176.5 (2)
C1—N1—C11—C12−35.8 (4)C21—C22—C23—O2−176.9 (3)
C1—N1—C11—C16147.8 (3)C21—C22—C23—C241.9 (4)
C16—C11—C12—C130.3 (4)C28—O3—C24—C25111.7 (3)
N1—C11—C12—C13−176.0 (3)C28—O3—C24—C23−72.5 (4)
C11—C12—C13—C14−1.2 (4)O2—C23—C24—O31.4 (4)
C11—C12—C13—Br1176.5 (2)C22—C23—C24—O3−177.5 (3)
C12—C13—C14—C151.5 (5)O2—C23—C24—C25177.1 (2)
Br1—C13—C14—C15−176.2 (2)C22—C23—C24—C25−1.8 (4)
C13—C14—C15—C16−1.0 (5)C29—O4—C25—C26−2.5 (4)
C14—C15—C16—C110.2 (5)C29—O4—C25—C24177.7 (3)
C12—C11—C16—C150.2 (4)O3—C24—C25—O4−4.4 (4)
N1—C11—C16—C15176.6 (3)C23—C24—C25—O4179.8 (2)
O1—C1—C21—C26−146.1 (3)O3—C24—C25—C26175.8 (3)
N1—C1—C21—C2634.6 (4)C23—C24—C25—C260.0 (4)
O1—C1—C21—C2232.5 (4)O4—C25—C26—C21−178.2 (2)
N1—C1—C21—C22−146.8 (3)C24—C25—C26—C211.6 (4)
C26—C21—C22—C23−0.3 (4)C22—C21—C26—C25−1.5 (4)
C1—C21—C22—C23−178.9 (2)C1—C21—C26—C25177.1 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.85 (4)2.06 (4)2.821 (3)149 (3)

Symmetry codes: (i) x, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2213).

References

  • Blessing, R. H. (1995). Acta Cryst. A51, 33–38. [PubMed]
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Saeed, A., Irfan, M. & Bolte, M. (2009). Acta Cryst. E65, o1334. [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]
  • Stoe & Cie (2001). X-AREA Stoe & Cie, Darmstadt, Germany.
  • Vande Velde, C., Bultinck, E., Tersago, K., Van Alsenoy, C. & Blockhuys, F. (2006). Int. J. Quantum Chem.107, 670–679.

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