2-(4-Methoxy­phen­yl)-6-trifluoro­methyl-1H-pyrrolo[3,2-c]quinoline monohydrate

Grzegorz Dutkiewicz; Anil N Mayekar; H S Yathirajan; B Narayana; Maciej Kubicki

doi:10.1107/S1600536810013644

. 2010 Apr 17;66(Pt 5):o1111–o1112. doi: 10.1107/S1600536810013644

2-(4-Methoxyphenyl)-6-trifluoromethyl-1H-pyrrolo[3,2-c]quinoline monohydrate

Grzegorz Dutkiewicz ^a, Anil N Mayekar ^b, H S Yathirajan ^b, B Narayana ^c, Maciej Kubicki ^a,^*

PMCID: PMC2979020 PMID: 21579163

Abstract

In the title compound, C₁₉H₁₃F₃N₂O·H₂O, the phenyl and pyrroloquinoline ring system are close to coplanar [dihedral angle = 10.94 (4)°]. The methoxy group also is almost coplanar with the phenyl ring [5.4 (1)°]. In the crystal structure N—H⋯O(water) and water–quinoline O—H⋯N hydrogen bonds build up a supramolecular chain-like arrangement along [001]. The remaining H atom of the water molecule does not take part in classical hydrogen bonds. Instead, this O—H bond points toward the center of the phenyl ring of a neighbouring molecule. Weak C—H⋯O and C—H⋯π interactions are also present.

Related literature

For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For O—H⋯π bonds, see: Atwood et al. (1991 ▶). For the graph-set description of hydrogen-bond systems, see: Bernstein et al. (1995 ▶). For the influence of substituents on the geometry of aromatic rings, see: Domenicano (1988 ▶). For a similar synthesis, see: Dutkiewicz et al. (2010 ▶). For related structures, see: Fan & Chen (1987 ▶); Lynch et al. (2001 ▶); Lynch & McClenaghan (2002 ▶).

Experimental

Crystal data

C₁₉H₁₃F₃N₂O·H₂O
M _r = 360.33
Monoclinic,
a = 13.838 (1) Å
b = 7.0432 (5) Å
c = 17.758 (2) Å
β = 102.743 (8)°
V = 1688.2 (2) Å³
Z = 4
Cu Kα radiation
μ = 0.99 mm⁻¹
T = 295 K
0.4 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction SuperNova (single source at offset) Atlas diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.340, T _max = 1.000
5601 measured reflections
3304 independent reflections
2767 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.128
S = 1.07
3304 reflections
296 parameters
All H-atom parameters refined
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810013644/im2190sup1.cif

e-66-o1111-sup1.cif^{(21KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013644/im2190Isup2.hkl

e-66-o1111-Isup2.hkl^{(158.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

CgA, CgB, CgD are the centroids of the C5–C9,C1C, N1,C2–C5,C1C and C14–C19 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1W	0.987 (19)	2.42 (2)	3.340 (2)	155 (2)
N11—H11⋯O1W	0.92 (2)	1.94 (2)	2.845 (2)	167 (2)
C19—H19⋯O1W	0.977 (19)	2.49 (2)	3.439 (2)	164 (1)
C8—H8⋯O20ⁱ	1.02 (2)	2.45 (2)	3.427 (2)	160 (2)
O1W—H1W1⋯N1ⁱⁱ	0.91 (2)	1.93 (2)	2.807 (2)	161 (2)
C21—H21C⋯CgAⁱⁱⁱ	0.94 (2)	2.83 (2)	3.550 (2)	135 (2)
C21—H21B⋯CgB^iv	0.97 (2)	2.72 (2)	3.503 (2)	138 (2)
O1W—H1W2⋯CgDⁱⁱⁱ	0.82 (3)	2.62 (3)	3.310 (2)	143 (2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

ANM thanks the University of Mysore for the research facilities.

supplementary crystallographic information

Comment

There is only one crystal structure of a compound having a pyrrolo[3,2-c]quinoline skeleton in the Cambridge Crystallographic Database (Allen, 2002; Version 5.31 of November 2009, last update Feb. 2010): 1-phenyl-2,3,4-tris(trifluoromethyl)pyrrolo[2,3-c]quinoline (Fan & Chen, 1987). The only other similar structurally characterized compounds are derivatives of 1H-pyrrolo[2,3-h]quinoline, namely 2-(4-pyridyl)-pyrrolo[3,2-h]quinoline (Lynch et al., 2001) and 2-phenylpyrrolo[2,3-h]quinoline dihydrate (Lynch & McClenaghan, 2002). Here we present the results of the crystal structure determination of 2-(4-methoxyphenyl)-6-(trifluoromethyl)-1H-pyrrolo[3,2-c]quinoline hydrate(1 . H₂O, Scheme 1).

Two planar systems in (1), pyrroloquinoline (planar within 0.0171 (4) Å) and the phenyl ring (0.0050 (11) Å) make a dihedral angle of 10.94 (4)°. Therefore, the complete molecule (without F atoms) is approximately planar. The methoxy group also is not twisted significantly (5.4 (1)°) with respect to the phenyl ring plane. Bond angles within the phenyl ring are influenced by the presence of substituents. As expected for p-disubstitution, the influences are almost additive. The sum of values given by Domenicano (1988) or found in the CSD for mono-substituted phenyl rings are very close to the actual values in (1).

The primary motif of the crystal packing is a chain of alternate water and 1 molecules (Fig. 2, Table 1). In that chain (C²₂(8) using graph set notation: Bernstein et al., 1995) both components act as hydrogen bond donor and acceptor. N11—H11 group of 1 donates hydrogen for the N—H···O1W (water) hydrogen bond, and the water molecule acts as a donor for the O—H···N1(quinoline) hydrogen bond. Due to the steric requirement, the O1W oxygen atom is also in close contact with the adjacent H6 and H19 hydrogen atoms. Because of the geometric parameters of these interactions (Table 1), they might be regarded as the secondary, weak hydrogen bonds. The remaining hydrogen atom of the water molecule does not take part in "classical" hydrogen bonds; instead this O—H bond points toward the phenyl ring of the neighbouring molecule, probably making the O—H(water)···π weak hydrogen bond. Such hydrogen bonds were described by Atwood et al. (1991), and they are supposed to play a role in the biological systems. There are some 300 cases of such short contacts in the CSD. In 1, O—H···π hydrogen bonds together with another weak interactions of C—H···O, C—H···π and π···π type, connect the neighbouring chains (Table 1, Fig. 3).

Experimental

1-(4-methoxyphenyl)ethanone [8-(trifluoromethyl)quinolin-4-yl]hydrazone (1.8 g, 5 mmoles), prepared according to the previously described method (Dutkiewicz et al., 2010) was added to 5 ml of diphenyl ether and the mixture was heated at 523 K in an oil bath for 6 hrs. After cooling, ether was added until the solution became cloudy. Further cooling resulted in precipitation of the product (I), which was collected by filtration. Recrystallization was performed at room temperature from ethanol, m.p.: 401-403 K. Analysis found: C 66.56, H 3.79, N 8.23%; C₁₉H₁₃F₃N₂O, requires: C 66.66, H 3.83, N 8.18%