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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o850.
Published online 2009 March 25. doi:  10.1107/S1600536809009283
PMCID: PMC2968993

2,2′-Diamino-N,N′-(o-phenyl­ene)di­benz­amide

Abstract

In the structure of the title compound, C20H18N4O2, the N—H and C=O bonds are trans to each other and the amide O atoms are syn to the ortho amino N atom in the benzoyl rings. The amide groups form dihedral angles of 8.4 (2) and 13.8 (2)° with their respective benzoyl rings, and dihedral angles of 51.85 (16) and 51.19 (17)° with the phenyl­enediamine ring. In the crystal, a centrosymmetric dimer is formed by inter­molecular N—H(...)O hydrogen bonds, resulting in an R 2 2(14) descriptor on a unitary level of graph-set analysis, and three intramolecular N—H(...)O bonds also occur.

Related literature

For the synthesis, see: Black & Rothnie (1983 [triangle]). For metal coordination, see: Booysen et al. (2008 [triangle]). For stereoselectivity in synthesis, see: Valik et al. (2002 [triangle]). For applications of polyamides, see: Kang et al. (2001 [triangle]). For related structures, see Gowda et al. (2003 [triangle], 2008 [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o850-scheme1.jpg

Experimental

Crystal data

  • C20H18N4O2
  • M r = 346.38
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o850-efi1.jpg
  • a = 8.7464 (3) Å
  • b = 14.4308 (6) Å
  • c = 13.6161 (6) Å
  • β = 97.291 (3)°
  • V = 1704.69 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 200 K
  • 0.16 × 0.14 × 0.10 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: none
  • 7575 measured reflections
  • 3893 independent reflections
  • 2085 reflections with I > 2σ(I)
  • R int = 0.049

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.122
  • S = 0.99
  • 3893 reflections
  • 308 parameters
  • All H-atom parameters refined
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: COLLECT (Nonius, 2004 [triangle]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO (Otwinowski & Minor, 1997 [triangle]) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: PLATON (Spek, 2009 [triangle]) and WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009283/sj2594sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009283/sj2594Isup2.hkl

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

Acknowledgments

The authors thank Professor P. Klüfers for generous allocation of diffractometer time.

supplementary crystallographic information

Comment

In the present work the structure of N,N'-(1,2-phenylene)bis(2-aminobenzamide) has been determined to explore its suitability as a tetradentate ligand for various metal ions. The conformations of N—H and C═O bonds in the amide groups are trans to each other (Fig. 1), similar to that observed in other benzamides and benzanilides (Gowda et al., 2003, 2008). Also, the conformations of the amide O atoms are syn to the ortho amino groups in the benzoyl rings. The amide group N1HC1O1 makes dihedral angles of 8.4 (2)° and 51.85 (16)° with the benzoyl and phenylene rings respectively. For the N3HC14O2 group, these values are 13.8 (2)° and 51.19 (17)°. The C2–C7 and C15–C20 benzoyl rings form dihedral angles of 59.64 (17)° and 64.86 (18)° respectively with the phenylene ring.

The conformational arrangement of the rings is mainly determined by intra- and intermolecular hydrogen-bonds. The graph set descriptor for the intramolecular hydrogen bonds is S(6)S(6)S(7) on a unitary level. Centrosymmetric dimers are formed by two intermolecular hydrogen bonds of the type N—H···O resulting in a R22(14) descriptor on a unitary level. The hydrogen bonding pattern is shown in Fig. 2.

Experimental

The title compound was prepared according to the literature method (Black & Rothnie, 1983). The purity of the compound was checked by determining its melting point. It was characterized by recording its IR and 1H NMR spectra. Single crystals of the title compound were obtained from a pyridine/ethanol (1:1, v/v) solution.

Refinement

The H atoms were located in the difference map, their positional and isotropic vibrational parameters were refined freely.

Figures

Fig. 1.
The molecular structure of the title compound (anisotropic displacement ellipsoids drawn at the 50% probability level).
Fig. 2.
Hydrogen bonds (dashed lines) determining the conformational arrangement of the rings. For details of the hydrogen bonds see Table 1.

Crystal data

C20H18N4O2F(000) = 728
Mr = 346.38Dx = 1.350 Mg m3
Monoclinic, P21/nMelting point: 532 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 8.7464 (3) ÅCell parameters from 12612 reflections
b = 14.4308 (6) Åθ = 3.1–27.5°
c = 13.6161 (6) ŵ = 0.09 mm1
β = 97.291 (3)°T = 200 K
V = 1704.69 (12) Å3Block, brown
Z = 40.16 × 0.14 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer2085 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.049
MONTEL, graded multilayered X-ray opticsθmax = 27.5°, θmin = 3.2°
Detector resolution: 9 pixels mm-1h = −11→11
CCD; rotation images; thick slices scansk = −18→18
7575 measured reflectionsl = −17→17
3893 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047All H-atom parameters refined
wR(F2) = 0.122w = 1/[σ2(Fo2) + (0.0521P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
3893 reflectionsΔρmax = 0.19 e Å3
308 parametersΔρmin = −0.19 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0130 (17)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.50757 (13)0.19967 (8)1.10126 (9)0.0426 (4)
O20.33370 (13)0.11696 (9)0.75452 (9)0.0431 (4)
N10.45030 (17)0.17105 (11)0.93824 (12)0.0371 (4)
N20.3038 (2)0.28860 (15)1.19702 (14)0.0599 (5)
N30.43678 (16)−0.00594 (12)0.84087 (11)0.0364 (4)
N40.1025 (3)0.08932 (14)0.61238 (15)0.0579 (5)
C10.41993 (19)0.21187 (12)1.02250 (14)0.0343 (4)
C20.27907 (18)0.27011 (11)1.01692 (13)0.0350 (4)
C30.2292 (2)0.30615 (13)1.10429 (15)0.0437 (5)
C40.0941 (2)0.35939 (15)1.0947 (2)0.0552 (6)
C50.0119 (2)0.37821 (15)1.00496 (19)0.0566 (6)
C60.0630 (2)0.34564 (15)0.91861 (18)0.0552 (6)
C70.1946 (2)0.29271 (14)0.92620 (16)0.0457 (5)
C80.58760 (18)0.12237 (12)0.92527 (12)0.0334 (4)
C90.57907 (18)0.03780 (12)0.87594 (12)0.0331 (4)
C100.7152 (2)−0.00822 (14)0.86314 (14)0.0408 (5)
C110.8571 (2)0.02948 (15)0.89720 (14)0.0451 (5)
C120.8644 (2)0.11444 (14)0.94410 (14)0.0422 (5)
C130.7312 (2)0.16123 (14)0.95732 (13)0.0377 (5)
C140.32233 (19)0.03407 (13)0.77899 (12)0.0346 (4)
C150.18663 (18)−0.02232 (12)0.74265 (12)0.0339 (4)
C160.0793 (2)0.00956 (13)0.66357 (13)0.0419 (5)
C17−0.0521 (2)−0.04422 (16)0.63397 (16)0.0501 (5)
C18−0.0768 (2)−0.12620 (16)0.67972 (17)0.0515 (6)
C190.0285 (2)−0.15877 (15)0.75605 (16)0.0480 (5)
C200.1582 (2)−0.10711 (13)0.78674 (15)0.0408 (5)
H130.7350 (18)0.2213 (13)0.9913 (13)0.043 (5)*
H200.2287 (19)−0.1285 (12)0.8428 (13)0.044 (5)*
H10.3885 (19)0.1773 (13)0.8853 (13)0.040 (6)*
H100.7102 (18)−0.0671 (13)0.8292 (12)0.041 (5)*
H120.960 (2)0.1435 (12)0.9685 (13)0.047 (5)*
H30.435 (2)−0.0647 (15)0.8504 (13)0.044 (6)*
H110.951 (2)−0.0045 (13)0.8853 (15)0.062 (6)*
H5−0.083 (2)0.4151 (14)1.0036 (13)0.059 (6)*
H17−0.132 (2)−0.0200 (13)0.5784 (14)0.056 (6)*
H18−0.168 (2)−0.1625 (14)0.6568 (14)0.056 (6)*
H70.231 (2)0.2720 (13)0.8671 (15)0.050 (5)*
H40.063 (2)0.3824 (14)1.1515 (16)0.068 (7)*
H190.011 (2)−0.2158 (14)0.7871 (13)0.052 (6)*
H410.027 (3)0.1085 (16)0.5717 (18)0.076 (8)*
H60.010 (2)0.3612 (14)0.8493 (17)0.076 (7)*
H420.178 (3)0.1311 (17)0.647 (2)0.090 (8)*
H210.405 (3)0.2631 (16)1.2012 (17)0.083 (8)*
H220.288 (3)0.3284 (19)1.2441 (19)0.090 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0509 (8)0.0387 (8)0.0375 (8)0.0062 (6)0.0034 (6)−0.0021 (6)
O20.0499 (8)0.0374 (8)0.0412 (8)−0.0016 (6)0.0027 (6)0.0061 (6)
N10.0371 (9)0.0387 (10)0.0349 (10)0.0081 (7)0.0030 (7)−0.0038 (8)
N20.0682 (14)0.0678 (14)0.0466 (12)0.0046 (10)0.0183 (10)−0.0122 (10)
N30.0359 (9)0.0300 (10)0.0427 (10)0.0037 (7)0.0025 (7)0.0016 (8)
N40.0608 (12)0.0560 (13)0.0524 (12)0.0074 (10)−0.0109 (10)0.0137 (10)
C10.0402 (10)0.0275 (10)0.0362 (11)−0.0034 (8)0.0095 (9)0.0002 (8)
C20.0378 (10)0.0266 (10)0.0423 (11)0.0012 (8)0.0113 (8)0.0010 (8)
C30.0472 (11)0.0365 (12)0.0508 (13)−0.0022 (9)0.0190 (10)−0.0027 (9)
C40.0543 (13)0.0481 (14)0.0689 (17)0.0041 (11)0.0304 (13)−0.0071 (12)
C50.0436 (12)0.0419 (13)0.0876 (19)0.0088 (10)0.0206 (13)0.0030 (12)
C60.0478 (12)0.0506 (14)0.0675 (16)0.0117 (10)0.0088 (11)0.0100 (12)
C70.0450 (11)0.0459 (13)0.0481 (13)0.0087 (9)0.0135 (10)0.0040 (10)
C80.0332 (9)0.0344 (11)0.0333 (10)0.0045 (8)0.0072 (7)0.0033 (8)
C90.0343 (10)0.0332 (11)0.0318 (10)0.0030 (8)0.0048 (7)0.0029 (8)
C100.0428 (11)0.0397 (12)0.0410 (12)0.0073 (9)0.0089 (9)−0.0009 (9)
C110.0380 (11)0.0521 (14)0.0462 (13)0.0092 (10)0.0093 (9)0.0028 (10)
C120.0336 (11)0.0521 (14)0.0409 (12)−0.0017 (10)0.0043 (9)0.0058 (10)
C130.0400 (11)0.0370 (12)0.0364 (11)−0.0004 (9)0.0054 (8)0.0022 (9)
C140.0388 (10)0.0367 (12)0.0302 (10)0.0053 (9)0.0114 (8)0.0008 (9)
C150.0363 (10)0.0355 (11)0.0303 (10)0.0035 (8)0.0061 (8)−0.0022 (8)
C160.0456 (11)0.0428 (13)0.0370 (12)0.0075 (9)0.0041 (9)−0.0029 (9)
C170.0438 (12)0.0540 (15)0.0498 (14)0.0046 (11)−0.0045 (10)−0.0093 (11)
C180.0405 (12)0.0522 (15)0.0613 (15)−0.0014 (11)0.0038 (10)−0.0189 (12)
C190.0451 (12)0.0421 (13)0.0580 (14)−0.0019 (10)0.0113 (10)−0.0032 (11)
C200.0406 (11)0.0416 (12)0.0403 (12)0.0018 (9)0.0055 (9)−0.0002 (9)

Geometric parameters (Å, °)

O1—C11.249 (2)C6—H61.02 (2)
O2—C141.249 (2)C7—H70.95 (2)
N1—C11.346 (2)C8—C91.390 (2)
N1—C81.421 (2)C8—C131.394 (2)
N1—H10.849 (17)C9—C101.394 (2)
N2—C31.369 (3)C10—C111.380 (3)
N2—H210.95 (2)C10—H100.966 (19)
N2—H220.89 (3)C11—C121.380 (3)
N3—C141.353 (2)C11—H110.986 (19)
N3—C91.423 (2)C12—C131.378 (3)
N3—H30.86 (2)C12—H120.957 (18)
N4—C161.374 (2)C13—H130.981 (18)
N4—H410.85 (2)C14—C151.472 (2)
N4—H420.97 (3)C15—C201.399 (2)
C1—C21.485 (2)C15—C161.413 (2)
C2—C71.395 (3)C16—C171.403 (3)
C2—C31.417 (2)C17—C181.367 (3)
C3—C41.402 (3)C17—H171.024 (19)
C4—C51.364 (3)C18—C191.380 (3)
C4—H40.91 (2)C18—H180.97 (2)
C5—C61.391 (3)C19—C201.378 (3)
C5—H50.98 (2)C19—H190.945 (19)
C6—C71.374 (3)C20—H200.968 (18)
C1—N1—C8125.70 (16)C8—C9—C10118.97 (16)
C1—N1—H1120.3 (12)C8—C9—N3122.85 (14)
C8—N1—H1113.8 (12)C10—C9—N3118.14 (17)
C3—N2—H21117.2 (14)C11—C10—C9121.07 (19)
C3—N2—H22116.6 (16)C11—C10—H10119.5 (10)
H21—N2—H22116 (2)C9—C10—H10119.4 (10)
C14—N3—C9124.48 (17)C10—C11—C12119.55 (18)
C14—N3—H3119.2 (12)C10—C11—H11118.6 (11)
C9—N3—H3114.9 (12)C12—C11—H11121.8 (11)
C16—N4—H41116.7 (15)C13—C12—C11120.32 (18)
C16—N4—H42114.2 (15)C13—C12—H12117.2 (11)
H41—N4—H42122 (2)C11—C12—H12122.5 (11)
O1—C1—N1120.28 (16)C12—C13—C8120.35 (19)
O1—C1—C2122.57 (16)C12—C13—H13121.0 (10)
N1—C1—C2117.15 (16)C8—C13—H13118.6 (10)
C7—C2—C3118.21 (17)O2—C14—N3119.81 (16)
C7—C2—C1121.35 (16)O2—C14—C15121.86 (16)
C3—C2—C1120.42 (16)N3—C14—C15118.33 (17)
N2—C3—C4118.99 (19)C20—C15—C16118.35 (17)
N2—C3—C2123.05 (17)C20—C15—C14121.25 (16)
C4—C3—C2117.92 (19)C16—C15—C14120.38 (17)
C5—C4—C3122.4 (2)N4—C16—C17119.08 (19)
C5—C4—H4120.6 (13)N4—C16—C15122.20 (18)
C3—C4—H4117.0 (13)C17—C16—C15118.67 (19)
C4—C5—C6120.0 (2)C18—C17—C16121.3 (2)
C4—C5—H5118.2 (11)C18—C17—H17120.0 (10)
C6—C5—H5121.8 (11)C16—C17—H17118.7 (10)
C7—C6—C5118.7 (2)C17—C18—C19120.6 (2)
C7—C6—H6118.2 (12)C17—C18—H18119.4 (11)
C5—C6—H6123.1 (12)C19—C18—H18120.0 (11)
C6—C7—C2122.8 (2)C20—C19—C18119.3 (2)
C6—C7—H7118.4 (11)C20—C19—H19120.4 (11)
C2—C7—H7118.8 (11)C18—C19—H19120.3 (11)
C9—C8—C13119.69 (15)C19—C20—C15121.82 (19)
C9—C8—N1119.96 (15)C19—C20—H20118.9 (10)
C13—C8—N1120.27 (16)C15—C20—H20119.1 (10)
C8—N1—C1—O1−8.7 (3)C8—C9—C10—C11−1.0 (3)
C8—N1—C1—C2171.86 (15)N3—C9—C10—C11−178.69 (17)
O1—C1—C2—C7171.32 (17)C9—C10—C11—C12−0.5 (3)
N1—C1—C2—C7−9.2 (2)C10—C11—C12—C130.3 (3)
O1—C1—C2—C3−7.1 (3)C11—C12—C13—C81.3 (3)
N1—C1—C2—C3172.34 (16)C9—C8—C13—C12−2.8 (3)
C7—C2—C3—N2−179.81 (18)N1—C8—C13—C12−179.49 (16)
C1—C2—C3—N2−1.3 (3)C9—N3—C14—O2−5.0 (2)
C7—C2—C3—C42.6 (3)C9—N3—C14—C15175.18 (14)
C1—C2—C3—C4−178.97 (16)O2—C14—C15—C20−165.42 (16)
N2—C3—C4—C5−178.67 (19)N3—C14—C15—C2014.4 (2)
C2—C3—C4—C5−0.9 (3)O2—C14—C15—C1612.8 (2)
C3—C4—C5—C6−1.2 (3)N3—C14—C15—C16−167.37 (15)
C4—C5—C6—C71.6 (3)C20—C15—C16—N4−176.21 (16)
C5—C6—C7—C20.1 (3)C14—C15—C16—N45.5 (3)
C3—C2—C7—C6−2.2 (3)C20—C15—C16—C171.1 (3)
C1—C2—C7—C6179.34 (17)C14—C15—C16—C17−177.18 (14)
C1—N1—C8—C9135.32 (18)N4—C16—C17—C18177.07 (18)
C1—N1—C8—C13−48.0 (3)C15—C16—C17—C18−0.3 (3)
C13—C8—C9—C102.6 (2)C16—C17—C18—C19−0.7 (3)
N1—C8—C9—C10179.31 (16)C17—C18—C19—C200.8 (3)
C13—C8—C9—N3−179.83 (16)C18—C19—C20—C150.0 (3)
N1—C8—C9—N3−3.1 (2)C16—C15—C20—C19−1.0 (3)
C14—N3—C9—C855.6 (2)C14—C15—C20—C19177.33 (16)
C14—N3—C9—C10−126.74 (18)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O20.849 (17)1.986 (18)2.694 (2)140.4 (17)
N3—H3···O1i0.86 (2)2.10 (2)2.929 (2)163.0 (17)
N4—H42···O20.97 (3)1.88 (3)2.646 (3)134 (2)
N2—H21···O10.95 (2)1.95 (2)2.667 (2)130.2 (19)

Symmetry codes: (i) −x+1, −y, −z+2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2594).

References

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