PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2527.
Published online 2009 September 26. doi:  10.1107/S1600536809034710
PMCID: PMC2970402

2,4-Dichloro-N-p-tolyl­benzamide

Abstract

In the title compound, C14H11Cl2NO, the C—N—C(=O)—C amide unit is almost planar (r.m.s. deviation = 0.0317 Å) and subtends dihedral angles of 65.93 (6) and 29.45 (7)°, respectively, to the dichloro­benzene and tolyl rings. The two aromatic rings are inclined at 37.92 (6)° to one another. In the crystal structure, N—H(...)O hydrogen bonds link the mol­ecules into chains along b. Additional weak C—H(...)Cl and C—H(...)O hydrogen bonds combine with C—H(...)π and very weak π–π contacts [Cg(...)Cg distance = 4.0217 (12) Å] to stack the mol­ecules down b.

Related literature

For background to our work on benzamide derivatives, see: Saeed et al. (2008 [triangle]). For related structures see: Zhou & Zheng (2007 [triangle]); Gowda et al. (2008a [triangle],b [triangle],c [triangle], 2009 [triangle]); Chopra & Guru Row (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2527-scheme1.jpg

Experimental

Crystal data

  • C14H11Cl2NO
  • M r = 280.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2527-efi1.jpg
  • a = 9.0884 (18) Å
  • b = 9.825 (2) Å
  • c = 14.167 (3) Å
  • β = 94.208 (9)°
  • V = 1261.6 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.50 mm−1
  • T = 89 K
  • 0.33 × 0.26 × 0.06 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2006 [triangle]) T min = 0.753, T max = 0.970
  • 20982 measured reflections
  • 4465 independent reflections
  • 3463 reflections with I > 2σ(I)
  • R int = 0.044

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.132
  • S = 1.15
  • 4465 reflections
  • 167 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.57 e Å−3
  • Δρmin = −0.49 e Å−3

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: APEX2 and SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]) and TITAN2000 (Hunter & Simpson, 1999 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 [triangle]), PLATON (Spek, 2009 [triangle]) and publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034710/fl2252sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034710/fl2252Isup2.hkl

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

Acknowledgments

We thank the University of Otago for purchase of the diffractometer.

supplementary crystallographic information

Comment

The background to our work on benzamide derivatives has been described in a previous paper (Saeed et al., 2008). In the title compound (I), Fig. 1, the C8–N1–C1(O1)–C2 amide unit is planar, r.m.s. deviation 0.0317 Å, and subtends dihedral angles of 65.93 (6)° and 29.45 (7)° respectively to the C2···C7 dichlorobenzene and C8···C13 tolyl rings. The two aromatic rings are inclined at 37.92 (6)° to one another. Bond distances within the molecule are normal and similar to those observed in comparable structures (Zhou & Zheng, 2007; Gowda et al. 2008a,b,c 2009; Chopra & Guru Row, 2005).

In the crystal structure N—H···O hydrogen bonds link molecules in a head to tail fashion into rows along b. C7—H7···π and weak, inversion related π–π contacts involving adjacent dichlorobenene rings [Cg···Cg distance 4.0217 (12), symmetry operation 1 - x, 1 - y, 1 - z] are also observed, Table 1, Fig 2. These together with additional C—H···Cl and C—H···O hydrogen bonds link the stacks of molecules alternately head to head and head to tail down the b axis, Fig. 3.

Experimental

2,4-Dichlorobenzoyl chloride (5.4 mmol) in CHCl3 was treated with p-toluidine(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 by evaporation from CHCl3 afforded the title compound (84%) as colourless needles: Anal. calcd. for C14H11Cl2NO,: C, 60.02; H, 3.96; N, 5.00%; found: C, 60.06; H, 3.92; N, 5.10%

Refinement

The H atom bound to N1 was located in a difference Fourier map and its coordinates were refined with Uiso=1.2Ueq (N). All other H-atoms were placed in calculated positions and refined using a riding model with d(C—H) = 0.95 Å, Uiso=1.2Ueq (C) for aromatic and 0.98 Å, Uiso = 1.5Ueq (C) for CH3 H atoms.

Figures

Fig. 1.
The structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level.
Fig. 2.
π–π and C—H···π interactions in (I). Contacts are shown as dotted lines,the coloured spheres represent the ring centroids.
Fig. 3.
Crystal packing of (I) viewed down the b axis, with hydrogen bonds drawn as dashed lines.

Crystal data

C14H11Cl2NOF(000) = 576
Mr = 280.14Dx = 1.475 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5859 reflections
a = 9.0884 (18) Åθ = 2.5–33.0°
b = 9.825 (2) ŵ = 0.50 mm1
c = 14.167 (3) ÅT = 89 K
β = 94.208 (9)°Irregular fragment, colourless
V = 1261.6 (4) Å30.33 × 0.26 × 0.06 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer4465 independent reflections
Radiation source: fine-focus sealed tube3463 reflections with I > 2σ(I)
graphiteRint = 0.044
ω scansθmax = 33.1°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2006)h = −13→13
Tmin = 0.753, Tmax = 0.970k = −14→13
20982 measured reflectionsl = −21→21

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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H atoms treated by a mixture of independent and constrained refinement
S = 1.15w = 1/[σ2(Fo2) + (0.0688P)2 + 0.2064P] where P = (Fo2 + 2Fc2)/3
4465 reflections(Δ/σ)max = 0.001
167 parametersΔρmax = 0.57 e Å3
0 restraintsΔρmin = −0.48 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
C10.52742 (16)0.71474 (14)0.71812 (10)0.0111 (3)
C20.43510 (16)0.67111 (13)0.63071 (10)0.0105 (3)
C30.29263 (16)0.61878 (14)0.63334 (10)0.0121 (3)
C40.21096 (16)0.57806 (14)0.55106 (10)0.0126 (3)
H40.11470.54140.55390.015*
C50.27317 (16)0.59219 (14)0.46479 (10)0.0125 (3)
C60.41328 (16)0.64737 (14)0.45883 (10)0.0130 (3)
H60.45360.65840.39930.016*
C70.49281 (16)0.68595 (14)0.54224 (11)0.0125 (3)
H70.58870.72330.53910.015*
C80.66786 (16)0.62192 (14)0.86070 (10)0.0109 (3)
C90.77909 (17)0.71922 (15)0.87165 (11)0.0141 (3)
H90.79020.78550.82390.017*
C100.87396 (17)0.71820 (15)0.95361 (11)0.0153 (3)
H100.94980.78470.96070.018*
C110.86130 (16)0.62256 (14)1.02572 (11)0.0131 (3)
C120.74965 (17)0.52520 (15)1.01274 (11)0.0142 (3)
H120.73880.45851.06030.017*
C130.65393 (16)0.52412 (14)0.93137 (10)0.0123 (3)
H130.57890.45680.92380.015*
C140.96308 (18)0.62590 (17)1.11523 (11)0.0184 (3)
H14A0.91200.66831.16620.028*
H14B1.05150.67881.10400.028*
H14C0.99160.53281.13340.028*
N10.56897 (14)0.61267 (12)0.77821 (9)0.0120 (2)
O10.56444 (13)0.83472 (10)0.72985 (8)0.0168 (2)
Cl10.20933 (4)0.60815 (4)0.73967 (3)0.01815 (11)
Cl20.17246 (4)0.53821 (4)0.36221 (3)0.01910 (11)
H1N0.530 (2)0.534 (2)0.7672 (16)0.023*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0116 (6)0.0104 (6)0.0112 (6)0.0005 (5)0.0004 (5)0.0007 (5)
C20.0122 (6)0.0073 (6)0.0117 (6)0.0008 (4)−0.0010 (5)0.0009 (4)
C30.0135 (6)0.0120 (6)0.0107 (6)0.0020 (5)0.0011 (5)0.0023 (5)
C40.0108 (6)0.0127 (6)0.0141 (7)−0.0008 (5)−0.0005 (5)0.0009 (5)
C50.0145 (6)0.0111 (6)0.0115 (6)0.0015 (5)−0.0020 (5)−0.0012 (5)
C60.0154 (6)0.0114 (6)0.0123 (6)0.0003 (5)0.0022 (5)0.0005 (5)
C70.0127 (6)0.0095 (6)0.0153 (7)−0.0011 (5)0.0005 (5)0.0005 (5)
C80.0121 (6)0.0091 (6)0.0112 (6)0.0016 (4)−0.0006 (5)−0.0013 (4)
C90.0154 (6)0.0127 (6)0.0137 (6)−0.0026 (5)−0.0014 (5)0.0035 (5)
C100.0141 (7)0.0134 (6)0.0179 (7)−0.0031 (5)−0.0015 (6)0.0003 (5)
C110.0117 (6)0.0141 (6)0.0133 (6)0.0011 (5)−0.0008 (5)−0.0002 (5)
C120.0166 (7)0.0131 (6)0.0125 (6)−0.0014 (5)−0.0008 (5)0.0026 (5)
C130.0130 (6)0.0103 (6)0.0134 (6)−0.0019 (5)−0.0001 (5)0.0005 (5)
C140.0182 (7)0.0217 (7)0.0145 (7)−0.0031 (6)−0.0037 (6)0.0012 (6)
N10.0154 (6)0.0084 (5)0.0115 (6)−0.0014 (4)−0.0034 (5)0.0006 (4)
O10.0210 (6)0.0084 (5)0.0199 (5)−0.0009 (4)−0.0056 (4)0.0009 (4)
Cl10.01473 (18)0.0284 (2)0.01157 (18)0.00040 (13)0.00261 (13)0.00371 (13)
Cl20.01772 (19)0.0254 (2)0.01362 (18)−0.00149 (13)−0.00263 (14)−0.00494 (13)

Geometric parameters (Å, °)

C1—O11.2338 (17)C8—C131.400 (2)
C1—N11.3512 (18)C8—N11.4240 (18)
C1—C21.5062 (19)C9—C101.395 (2)
C2—C31.396 (2)C9—H90.9500
C2—C71.401 (2)C10—C111.399 (2)
C3—C41.394 (2)C10—H100.9500
C3—Cl11.7379 (16)C11—C121.397 (2)
C4—C51.391 (2)C11—C141.514 (2)
C4—H40.9500C12—C131.392 (2)
C5—C61.392 (2)C12—H120.9500
C5—Cl21.7423 (15)C13—H130.9500
C6—C71.392 (2)C14—H14A0.9800
C6—H60.9500C14—H14B0.9800
C7—H70.9500C14—H14C0.9800
C8—C91.392 (2)N1—H1N0.86 (2)
O1—C1—N1124.29 (13)C8—C9—C10119.17 (13)
O1—C1—C2120.84 (12)C8—C9—H9120.4
N1—C1—C2114.82 (12)C10—C9—H9120.4
C3—C2—C7118.10 (13)C9—C10—C11122.27 (14)
C3—C2—C1122.99 (13)C9—C10—H10118.9
C7—C2—C1118.90 (13)C11—C10—H10118.9
C4—C3—C2121.42 (14)C12—C11—C10117.50 (13)
C4—C3—Cl1117.94 (12)C12—C11—C14121.22 (14)
C2—C3—Cl1120.61 (11)C10—C11—C14121.27 (13)
C5—C4—C3118.71 (14)C13—C12—C11121.19 (14)
C5—C4—H4120.6C13—C12—H12119.4
C3—C4—H4120.6C11—C12—H12119.4
C4—C5—C6121.66 (13)C12—C13—C8120.20 (13)
C4—C5—Cl2118.69 (11)C12—C13—H13119.9
C6—C5—Cl2119.65 (12)C8—C13—H13119.9
C7—C6—C5118.36 (14)C11—C14—H14A109.5
C7—C6—H6120.8C11—C14—H14B109.5
C5—C6—H6120.8H14A—C14—H14B109.5
C6—C7—C2121.72 (13)C11—C14—H14C109.5
C6—C7—H7119.1H14A—C14—H14C109.5
C2—C7—H7119.1H14B—C14—H14C109.5
C9—C8—C13119.66 (13)C1—N1—C8126.87 (12)
C9—C8—N1123.01 (13)C1—N1—H1N117.5 (14)
C13—C8—N1117.28 (12)C8—N1—H1N115.6 (14)
O1—C1—C2—C3−115.79 (17)C1—C2—C7—C6179.87 (12)
N1—C1—C2—C366.64 (18)C13—C8—C9—C10−0.6 (2)
O1—C1—C2—C762.85 (19)N1—C8—C9—C10−178.01 (14)
N1—C1—C2—C7−114.72 (15)C8—C9—C10—C11−0.1 (2)
C7—C2—C3—C42.0 (2)C9—C10—C11—C120.6 (2)
C1—C2—C3—C4−179.31 (13)C9—C10—C11—C14−178.33 (15)
C7—C2—C3—Cl1−175.69 (10)C10—C11—C12—C13−0.5 (2)
C1—C2—C3—Cl12.96 (19)C14—C11—C12—C13178.50 (14)
C2—C3—C4—C5−0.9 (2)C11—C12—C13—C8−0.2 (2)
Cl1—C3—C4—C5176.86 (11)C9—C8—C13—C120.8 (2)
C3—C4—C5—C6−0.9 (2)N1—C8—C13—C12178.32 (13)
C3—C4—C5—Cl2178.77 (11)O1—C1—N1—C8−4.3 (2)
C4—C5—C6—C71.5 (2)C2—C1—N1—C8173.21 (13)
Cl2—C5—C6—C7−178.17 (11)C9—C8—N1—C1−26.7 (2)
C5—C6—C7—C2−0.3 (2)C13—C8—N1—C1155.92 (15)
C3—C2—C7—C6−1.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.86 (2)2.14 (2)2.9867 (17)168 (2)
C12—H12···Cl1ii0.952.913.7372 (17)146
C6—H6···O1iii0.952.673.619 (2)175
C7—H7···Cg2iv0.952.653.4865 (17)147

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, −y+1, −z+2; (iii) x, −y+3/2, z−1/2; (iv) x, −y+3/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FL2252).

References

  • Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst.37, 335–338.
  • Bruker (2006). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chopra, D. & Guru Row, T. N. (2005). J. Mol. Struct.733, 133–141.
  • Gowda, B. T., Tokarčík, M., Kožíšek, J., Chaithanya, U. & Fuess, H. (2009). Acta Cryst. E65, o630. [PMC free article] [PubMed]
  • Gowda, B. T., Tokarčík, M., Kožíšek, J. & Sowmya, B. P. (2008a). Acta Cryst. E64, o83.
  • Gowda, B. T., Tokarčík, M., Kožíšek, J., Sowmya, B. P. & Fuess, H. (2008b). Acta Cryst. E64, o340. [PMC free article] [PubMed]
  • Gowda, B. T., Tokarčík, M., Kožíšek, J., Sowmya, B. P. & Fuess, H. (2008c). Acta Cryst. E64, o1494. [PMC free article] [PubMed]
  • Hunter, K. A. & Simpson, J. (1999). TITAN2000 University of Otago, New Zealand.
  • Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst.39, 453–457.
  • Saeed, A., Khera, R. A., Abbas, N., Simpson, J. & Stanley, R. G. (2008). Acta Cryst. E64, o1976. [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]
  • Westrip, S. P. (2009). publCIF In preparation.
  • Zhou, B. & Zheng, P.-W. (2007). Acta Cryst. E63, o4630.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography