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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): o1565.
Published online 2009 June 13. doi:  10.1107/S1600536809021886
PMCID: PMC2969432

2-(5,6-Di­hydro­benzimidazolo[1,2-c]quinazolin-6-yl)aniline methanol solvate

Abstract

In the structure of the title compound, C20H16N4·CH4O, the aniline ring forms dihedral angles of 89.9 (2) and 85.4 (2)° with the benzimidazole and benzene rings, respectively. The orientation of the aniline ring is mainly determined by strong hydrogen bonds between the amino group and the non-fused quinazoline N atom. Inter­molecular hydrogen bonds of the N—H(...)N—H(...)N type along [010] and the N—H(...)O—H(...)N type along [100] are formed, resulting in C 2 2(4) and C 2 2(10) descriptors, respectively, on a binary level of graph-set analysis. There are C—H(...)π contacts with H(...)π distances of 2.44 Å; however, no π-stacking is observed.

Related literature

For the synthesis of quinazolines, see: Kubicova et al. (2003 [triangle]); Niementowski (1895 [triangle]). For the conformation, see: Cuny et al. (1980 [triangle]); Williamson (1957 [triangle]).

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Object name is e-65-o1565-scheme1.jpg

Experimental

Crystal data

  • C20H16N4·CH4O
  • M r = 344.41
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1565-efi1.jpg
  • a = 9.3703 (2) Å
  • b = 5.1728 (1) Å
  • c = 35.5169 (9) Å
  • β = 91.3908 (14)°
  • V = 1721.02 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 200 K
  • 0.23 × 0.06 × 0.05 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: none
  • 9302 measured reflections
  • 3136 independent reflections
  • 2089 reflections with I > 2σ(I)
  • R int = 0.051

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.123
  • S = 1.08
  • 3136 reflections
  • 253 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • 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 for Windows (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2006 [triangle]); software used to prepare material for publication: PARST (Nardelli, 1995 [triangle]), publCIF (Westrip, 2008 [triangle]) and WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809021886/bg2264sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021886/bg2264Isup2.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 2-(2,3,5,6-tetrahydrobenzimidazo[1,2-c]quinazolin-5-yl)benzenamine (Figure 1) has been determined to explore its suitability as a bidentate ligand for various metal ions. In the structure the quinazoline ring adopts a chair conformation: atoms C7, C8, C13, N2 and N3 are coplanar, with atom C14 departing from the plane by 0.2391 Å . The orientation of the aniline ring is mainly determined by a series of hydrogen-bonds between NH2 and NH groups, and between the phenylamino group and the quinazoline nitrogen (Figure 1 and Table 1). This ring makes dihedral angles of 89.9 (2)° and 85.4 (2)° with the benzimidazole and phenyl rings respectively. The ligand bond distances and angles show that N1—C7 is a localized double bond [1.321 (3) Å], with N2—C7 a single bond at 1.383 (3) Å. The N3—C14 bond length is 1.459 (3) Å, and the N3—C14—N2 bond angle [108.14 (17)°] illustrates the sp3 hybridization of C14. All the other bond lengths and angles in the molecule are normal.

Intermolecular hydrogen bonds of the N–H···N–H···N type along [010] and N–H···O–H···N along [100] are formed (Table 1) resulting in a C22(4) descriptor and a C22(10) descriptor on a binary level of graph set analysis, respectively. C–H···π contacts with H···Cg distances of 2.44 Å are presnt in the structure (Cg is the centre of gravity of ring C1 – C6); however, no π-stacking is observed.

Experimental

All chemicals used (reagent grade) were commercially available. A mass of 1.22 g (0.010 mol) of 2-aminobenzaldehyde was dissolved in methanol (50 cm3), and 2.09 g (0.010 mol) of 2-(2-aminophenyl)-1-benzimidazole was added with stirring. The mixture was heated under reflux for 2 h, then cooled to room temperature and filtered. The volume of the solution was reduced to ~ 10 cm3, and left to evaporate slowly at room temperature. After 2 days 2.48 g (72%) of colourless crystals, with the formulation C20H16N4.CH4O and suitable for X-ray analysis, were collected. M.p. 211°C. 1H NMR (300 MHz, d6-DMSO): 7.97 (1H,d), 7.62 (1H, d), 7.27 (1H, d), 7.25 (1H,t), 7.13 (2H, t), 6.97–7.02 (2H, m), 6.94 (1H, t), 6.86 (1H, t), 6.78 (1H, d), 6.61 (1H, d), 6.54(1H, t), 5.45 (2H, s), 3.18 (3H, s).

Refinement

All H atoms bonded to C atoms were calculated in idealized position and refined as riding on their parent atoms with Uiso(H) values of 1.2 Ueq(C). All H atoms bonded to N and O atoms were refined freely with individual Uiso(H) values.

Figures

Fig. 1.
The molecular structure of the title compound (anisotropic displacement ellipsoids drawn at the 50% probability level). Hydrogen bonds determining the conformational arrangement of the analine rings are also shown. Symmetry codes: (i): x, y+1, z; (ii) ...

Crystal data

C20H16N4·CH4OF(000) = 728
Mr = 344.41Dx = 1.329 (1) Mg m3
Monoclinic, P21/cMelting point: 484 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 9.3703 (2) ÅCell parameters from 41046 reflections
b = 5.1728 (1) Åθ = 3.1–25.4°
c = 35.5169 (9) ŵ = 0.09 mm1
β = 91.3908 (14)°T = 200 K
V = 1721.02 (7) Å3Rod, yellow
Z = 40.23 × 0.06 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer2089 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.051
MONTEL, graded multilayered X-ray opticsθmax = 25.4°, θmin = 3.2°
Detector resolution: 9 pixels mm-1h = −11→11
CCD; rotation images, [var phi] and ω scansk = −5→6
9302 measured reflectionsl = −42→42
3136 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)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.123w = 1/[σ2(Fo2) + (0.0417P)2 + 0.5855P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
3136 reflectionsΔρmax = 0.19 e Å3
253 parametersΔρmin = −0.19 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0138 (19)

Special details

Refinement. N- and O-bonded H: All H-atom parameters refined C-bonded H: H-atom parameters constrained

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

xyzUiso*/Ueq
O1−0.05660 (18)0.5134 (3)0.32314 (5)0.0506 (5)
H10.038 (3)0.482 (5)0.3324 (8)0.087 (10)*
N10.20470 (18)0.3599 (3)0.35685 (5)0.0349 (5)
N20.38507 (17)0.1319 (3)0.38325 (5)0.0321 (5)
N30.5138 (2)−0.1946 (4)0.35148 (5)0.0407 (5)
H3a0.564 (2)−0.350 (5)0.3544 (6)0.043 (7)*
N40.6823 (2)0.2995 (4)0.35560 (6)0.0381 (5)
H4a0.764 (3)0.364 (4)0.3436 (6)0.051 (7)*
H4b0.635 (2)0.195 (4)0.3412 (6)0.040 (7)*
C10.2283 (2)0.4419 (4)0.39363 (6)0.0329 (5)
C20.1591 (2)0.6363 (4)0.41352 (6)0.0394 (6)
H20.08630.73870.40190.047*
C30.2005 (2)0.6737 (5)0.45063 (7)0.0437 (6)
H30.15450.80370.46480.052*
C40.3083 (3)0.5254 (5)0.46794 (6)0.0443 (6)
H40.33320.55570.49370.053*
C50.3792 (2)0.3361 (4)0.44846 (6)0.0393 (6)
H50.45280.23600.46010.047*
C60.3383 (2)0.2981 (4)0.41099 (6)0.0317 (5)
C70.2981 (2)0.1726 (4)0.35178 (6)0.0307 (5)
C80.3146 (2)0.0110 (4)0.31914 (6)0.0321 (5)
C90.2270 (2)0.0334 (5)0.28675 (6)0.0410 (6)
H90.15720.16640.28530.049*
C100.2408 (3)−0.1347 (5)0.25705 (6)0.0475 (7)
H100.1800−0.12080.23540.057*
C110.3452 (3)−0.3251 (5)0.25931 (6)0.0452 (6)
H110.3552−0.44190.23890.054*
C120.4343 (2)−0.3483 (4)0.29040 (6)0.0393 (6)
H120.5060−0.47810.29120.047*
C130.4193 (2)−0.1808 (4)0.32092 (6)0.0333 (5)
C140.4874 (2)−0.0827 (4)0.38838 (6)0.0342 (5)
H140.4431−0.21780.40450.041*
C150.6265 (2)0.0014 (4)0.40688 (6)0.0322 (5)
C160.7166 (2)0.1831 (4)0.39045 (6)0.0337 (5)
C170.8413 (2)0.2541 (5)0.40991 (7)0.0423 (6)
H170.90130.38250.39960.051*
C180.8792 (3)0.1423 (5)0.44374 (7)0.0478 (7)
H180.96470.19480.45650.057*
C190.7947 (3)−0.0451 (5)0.45936 (7)0.0469 (6)
H190.8225−0.12650.48240.056*
C200.6682 (2)−0.1127 (4)0.44085 (6)0.0408 (6)
H200.6086−0.24000.45160.049*
C21−0.0816 (3)0.7792 (5)0.32160 (8)0.0677 (8)
H21A−0.01880.86710.34000.102*
H21B−0.18140.81410.32750.102*
H21C−0.06230.84300.29620.102*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0392 (11)0.0532 (12)0.0589 (11)0.0000 (9)−0.0085 (8)0.0070 (9)
N10.0293 (10)0.0331 (11)0.0421 (12)0.0012 (9)−0.0009 (8)−0.0012 (9)
N20.0292 (10)0.0293 (10)0.0378 (11)0.0002 (8)−0.0033 (8)−0.0017 (8)
N30.0379 (12)0.0347 (12)0.0491 (13)0.0077 (10)−0.0095 (9)−0.0094 (9)
N40.0321 (12)0.0386 (12)0.0435 (13)−0.0024 (10)0.0001 (10)0.0054 (10)
C10.0268 (12)0.0324 (13)0.0395 (13)−0.0056 (10)0.0006 (10)0.0001 (10)
C20.0307 (13)0.0357 (14)0.0519 (15)0.0003 (11)−0.0005 (11)−0.0032 (11)
C30.0395 (14)0.0424 (15)0.0494 (15)−0.0006 (12)0.0058 (11)−0.0098 (12)
C40.0479 (15)0.0436 (15)0.0415 (14)−0.0049 (13)0.0014 (11)−0.0057 (12)
C50.0403 (14)0.0372 (14)0.0401 (14)−0.0034 (11)−0.0028 (11)−0.0009 (11)
C60.0306 (12)0.0249 (12)0.0397 (13)−0.0049 (10)0.0021 (10)−0.0008 (10)
C70.0241 (12)0.0301 (13)0.0379 (13)−0.0050 (10)−0.0010 (9)0.0018 (10)
C80.0302 (12)0.0301 (13)0.0360 (13)−0.0063 (10)0.0022 (10)0.0023 (10)
C90.0403 (14)0.0437 (15)0.0388 (14)0.0016 (11)−0.0015 (11)0.0033 (11)
C100.0545 (17)0.0534 (17)0.0344 (14)0.0004 (13)−0.0033 (11)−0.0003 (12)
C110.0562 (16)0.0419 (15)0.0379 (14)−0.0036 (13)0.0077 (12)−0.0035 (11)
C120.0425 (14)0.0323 (14)0.0433 (14)0.0001 (11)0.0058 (11)0.0002 (11)
C130.0327 (13)0.0290 (13)0.0382 (13)−0.0061 (10)0.0016 (10)0.0028 (10)
C140.0314 (13)0.0280 (12)0.0432 (13)0.0016 (10)−0.0025 (10)0.0012 (10)
C150.0306 (12)0.0286 (12)0.0372 (13)0.0003 (10)−0.0019 (9)−0.0004 (10)
C160.0302 (12)0.0287 (13)0.0421 (13)0.0040 (10)−0.0001 (10)−0.0001 (10)
C170.0317 (13)0.0411 (14)0.0539 (15)−0.0051 (11)−0.0012 (11)0.0024 (12)
C180.0367 (14)0.0506 (16)0.0554 (16)−0.0008 (12)−0.0142 (12)−0.0053 (13)
C190.0464 (15)0.0485 (16)0.0451 (14)0.0009 (13)−0.0114 (12)0.0031 (12)
C200.0363 (13)0.0398 (14)0.0460 (14)−0.0013 (11)−0.0025 (11)0.0054 (11)
C210.0489 (17)0.055 (2)0.100 (2)−0.0015 (14)0.0074 (15)0.0046 (16)

Geometric parameters (Å, °)

O1—C211.395 (3)C8—C91.402 (3)
O1—H10.95 (3)C9—C101.376 (3)
N1—C71.320 (3)C9—H90.9500
N1—C11.386 (3)C10—C111.389 (3)
N2—C71.384 (3)C10—H100.9500
N2—C61.387 (3)C11—C121.373 (3)
N2—C141.475 (3)C11—H110.9500
N3—C131.386 (3)C12—C131.398 (3)
N3—C141.459 (3)C12—H120.9500
N3—H3a0.93 (2)C14—C151.509 (3)
N4—C161.406 (3)C14—H141.0000
N4—H4a0.95 (2)C15—C201.391 (3)
N4—H4b0.86 (2)C15—C161.400 (3)
C1—C21.397 (3)C16—C171.393 (3)
C1—C61.402 (3)C17—C181.372 (3)
C2—C31.379 (3)C17—H170.9500
C2—H20.9500C18—C191.377 (3)
C3—C41.399 (3)C18—H180.9500
C3—H30.9500C19—C201.386 (3)
C4—C51.379 (3)C19—H190.9500
C4—H40.9500C20—H200.9500
C5—C61.390 (3)C21—H21A0.9800
C5—H50.9500C21—H21B0.9800
C7—C81.441 (3)C21—H21C0.9800
C8—C131.396 (3)
C21—O1—H1109.6 (18)C11—C10—H10120.6
C7—N1—C1105.19 (17)C12—C11—C10121.5 (2)
C7—N2—C6106.81 (17)C12—C11—H11119.3
C7—N2—C14125.65 (17)C10—C11—H11119.3
C6—N2—C14126.49 (17)C11—C12—C13120.0 (2)
C13—N3—C14124.33 (19)C11—C12—H12120.0
C13—N3—H3a116.1 (13)C13—C12—H12120.0
C14—N3—H3a109.7 (13)N3—C13—C8120.48 (19)
C16—N4—H4a112.2 (13)N3—C13—C12120.1 (2)
C16—N4—H4b111.0 (15)C8—C13—C12119.29 (19)
H4a—N4—H4b111 (2)N3—C14—N2108.15 (16)
N1—C1—C2129.15 (19)N3—C14—C15110.02 (17)
N1—C1—C6110.53 (18)N2—C14—C15112.88 (17)
C2—C1—C6120.3 (2)N3—C14—H14108.6
C3—C2—C1117.5 (2)N2—C14—H14108.6
C3—C2—H2121.3C15—C14—H14108.6
C1—C2—H2121.3C20—C15—C16119.16 (19)
C2—C3—C4121.8 (2)C20—C15—C14118.47 (19)
C2—C3—H3119.1C16—C15—C14122.33 (19)
C4—C3—H3119.1C17—C16—C15118.5 (2)
C5—C4—C3121.4 (2)C17—C16—N4119.7 (2)
C5—C4—H4119.3C15—C16—N4121.82 (19)
C3—C4—H4119.3C18—C17—C16121.3 (2)
C4—C5—C6117.1 (2)C18—C17—H17119.3
C4—C5—H5121.4C16—C17—H17119.3
C6—C5—H5121.4C17—C18—C19120.7 (2)
N2—C6—C5133.1 (2)C17—C18—H18119.7
N2—C6—C1104.99 (17)C19—C18—H18119.7
C5—C6—C1121.9 (2)C18—C19—C20118.7 (2)
N1—C7—N2112.39 (18)C18—C19—H19120.7
N1—C7—C8128.31 (19)C20—C19—H19120.7
N2—C7—C8119.27 (19)C19—C20—C15121.5 (2)
C13—C8—C9119.5 (2)C19—C20—H20119.2
C13—C8—C7117.73 (18)C15—C20—H20119.2
C9—C8—C7122.7 (2)O1—C21—H21A109.5
C10—C9—C8120.9 (2)O1—C21—H21B109.5
C10—C9—H9119.6H21A—C21—H21B109.5
C8—C9—H9119.6O1—C21—H21C109.5
C9—C10—C11118.9 (2)H21A—C21—H21C109.5
C9—C10—H10120.6H21B—C21—H21C109.5
C7—N1—C1—C2179.8 (2)C10—C11—C12—C131.1 (3)
C7—N1—C1—C6−0.4 (2)C14—N3—C13—C821.6 (3)
N1—C1—C2—C3177.9 (2)C14—N3—C13—C12−162.73 (19)
C6—C1—C2—C3−1.9 (3)C9—C8—C13—N3175.3 (2)
C1—C2—C3—C40.5 (3)C7—C8—C13—N3−7.0 (3)
C2—C3—C4—C50.6 (4)C9—C8—C13—C12−0.4 (3)
C3—C4—C5—C6−0.4 (3)C7—C8—C13—C12177.30 (18)
C7—N2—C6—C5176.7 (2)C11—C12—C13—N3−176.6 (2)
C14—N2—C6—C58.0 (4)C11—C12—C13—C8−0.8 (3)
C7—N2—C6—C1−3.1 (2)C13—N3—C14—N2−24.8 (3)
C14—N2—C6—C1−171.81 (18)C13—N3—C14—C15−148.5 (2)
C4—C5—C6—N2179.3 (2)C7—N2—C14—N317.3 (3)
C4—C5—C6—C1−1.0 (3)C6—N2—C14—N3−176.03 (18)
N1—C1—C6—N22.2 (2)C7—N2—C14—C15139.21 (19)
C2—C1—C6—N2−178.01 (19)C6—N2—C14—C15−54.1 (3)
N1—C1—C6—C5−177.61 (18)N3—C14—C15—C20−118.8 (2)
C2—C1—C6—C52.2 (3)N2—C14—C15—C20120.3 (2)
C1—N1—C7—N2−1.7 (2)N3—C14—C15—C1659.1 (3)
C1—N1—C7—C8176.36 (19)N2—C14—C15—C16−61.8 (3)
C6—N2—C7—N13.1 (2)C20—C15—C16—C17−3.7 (3)
C14—N2—C7—N1171.95 (18)C14—C15—C16—C17178.5 (2)
C6—N2—C7—C8−175.15 (17)C20—C15—C16—N4178.1 (2)
C14—N2—C7—C8−6.3 (3)C14—C15—C16—N40.3 (3)
N1—C7—C8—C13−178.1 (2)C15—C16—C17—C182.6 (3)
N2—C7—C8—C13−0.2 (3)N4—C16—C17—C18−179.1 (2)
N1—C7—C8—C9−0.5 (3)C16—C17—C18—C190.3 (4)
N2—C7—C8—C9177.44 (19)C17—C18—C19—C20−2.1 (4)
C13—C8—C9—C101.4 (3)C18—C19—C20—C150.9 (4)
C7—C8—C9—C10−176.1 (2)C16—C15—C20—C192.0 (3)
C8—C9—C10—C11−1.2 (3)C14—C15—C20—C19179.9 (2)
C9—C10—C11—C120.0 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3a···N4i0.93 (2)2.13 (2)3.058 (3)174.5 (18)
N4—H4a···O1ii0.95 (2)2.00 (3)2.946 (3)174.4 (19)
N4—H4b···N30.86 (2)2.35 (2)3.006 (3)133.8 (19)
O1—H1···N10.95 (3)1.88 (3)2.814 (2)167 (3)
C14—H14···Cgi1.002.443.408 (2)162

Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BG2264).

References

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