Bis{4-[(Z)-N′-(4-hydroxy­benzyl­idene)hydrazino]-8-(trifluoro­meth­yl)quinolinium} sulfate dihydrate

Jerry P Jasinski; Ray J Butcher; B Narayana; K Sunil; H S Yathirajan

doi:10.1107/S1600536808000561

. 2008 Jan 23;64(Pt 2):o481–o482. doi: 10.1107/S1600536808000561

Bis{4-[(Z)-N′-(4-hydroxybenzylidene)hydrazino]-8-(trifluoromethyl)quinolinium} sulfate dihydrate

Jerry P Jasinski ^a,^*, Ray J Butcher ^b, B Narayana ^c, K Sunil ^c, H S Yathirajan ^d

PMCID: PMC2960448 PMID: 21201506

Abstract

The title compound, 2C₁₇H₁₃F₃N₃O⁺·SO₄ ²⁻·2H₂O, crystallizes with four independent cations (A, B, C and D) in the asymmetric unit, which is composed of two groups of two cations, one anion and two water molecules (Z′ = 2). The dihedral angle between the mean planes of the 4-hydroxyphenyl and quinolinium groups is 8.9 (7)° in A, 30.1 (6)° in B, 28.8 (8)° in C and 12.8 (1)° in D. The crystal packing is stabilized by intermolecular O—H⋯O and N—H⋯O hydrogen bonding between H atoms from 4-hydroxyphenyl O atoms and the O atoms of nearby water molecules and sulfate anions, as well as H atoms from the N atom of the hydrazino group to O atoms of neighboring sulfate anions, linking the components into chains with the 4-hydroxyphenyl and quinolinium rings parallel to the (011) plane. There is also an extensive array of intermolecular hydrogen bonds between water molecules themselves and with sulfate O atoms, as well as hydrogen-bond interactions between H atoms from the hydrazino group and sulfate O atoms. In addition, intermolecular π–π stacking interactions occur between nearby 4-hydroxyphenyl and quinolinium groups, with distances between the centroids of interacting rings in the range 3.4140 (9)–3.9659 (9) Å.

Related literature

For related structures, see: Yathirajan et al. (2007 ▶); Fun et al. (1999 ▶); Wang et al. (1998 ▶); Sadık et al. (2004 ▶). For related literature, see: Roma et al. (2000 ▶); Chen et al. (2001 ▶); Maguire et al. (1994 ▶); Zhang et al. (2000 ▶); Kahwa et al. (1986 ▶); Santos et al. (2001 ▶); Saim et al. (2004 ▶); El-Masry et al. (2000 ▶); Pandey et al. (1999 ▶); Hodnett et al. (1970 ▶); Misra et al. (1981 ▶); Varma et al. (1986 ▶); Singh et al. (1988 ▶); Desai et al. (2001 ▶).

Experimental

Crystal data

2C₁₇H₁₃F₃N₃O⁺·SO₄ ²⁻·2H₂O
M _r = 796.70
Monoclinic,
a = 13.4349 (1) Å
b = 23.8601 (1) Å
c = 21.7174 (1) Å
β = 96.8568 (4)°
V = 6911.89 (7) Å³
Z = 8
Cu Kα radiation
μ = 1.68 mm⁻¹
T = 200 (2) K
0.55 × 0.37 × 0.19 mm

Data collection

Oxford Diffraction Gemini R CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.441, T _max = 0.727
45529 measured reflections
13742 independent reflections
11290 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.127
S = 1.05
13742 reflections
1020 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: CrysAlisPro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlisPro; data reduction: CrysAlisPro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000561/nc2084sup1.cif

e-64-0o481-sup1.cif^{(49.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808000561/nc2084Isup2.hkl

e-64-0o481-Isup2.hkl^{(671.8KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4W—H4W1⋯O11ⁱ	0.835 (18)	2.23 (3)	2.986 (2)	151 (5)
N2A—H2AB⋯O11ⁱ	0.88	1.99	2.8592 (18)	170
C4A—H4AA⋯O11ⁱ	0.95	2.28	3.199 (2)	163
O1A—H1A⋯O12ⁱⁱ	0.84	1.89	2.6677 (18)	154
O1D—H1D⋯O13ⁱⁱ	0.84	1.75	2.5771 (17)	167
O4W—H4W2⋯O14ⁱⁱⁱ	0.820 (19)	2.06 (2)	2.860 (2)	167 (5)
C4D—H4DA⋯O14ⁱⁱⁱ	0.95	2.50	3.367 (2)	152
C11D—H11D⋯O14ⁱⁱⁱ	0.95	2.52	3.272 (2)	136
N1A—H1AA⋯O21ⁱ	0.88	2.06	2.8636 (18)	151
O3W—H3W2⋯O22ⁱ	0.841 (18)	2.039 (19)	2.864 (2)	167 (4)
N2B—H2BB⋯O22^iv	0.88	1.93	2.7909 (18)	166
C4B—H4BA⋯O22^iv	0.95	2.37	3.294 (2)	165
C11B—H11B⋯O22^iv	0.95	2.55	3.319 (2)	138
O3W—H3W1⋯O23ⁱⁱⁱ	0.824 (18)	1.952 (19)	2.776 (2)	179 (5)
O1W—H1W1⋯O24ⁱⁱⁱ	0.810 (17)	1.933 (17)	2.725 (2)	165 (3)
C8A—H8AA⋯O24ⁱ	0.95	2.39	3.134 (2)	135
C7C—H7CA⋯O1A^v	0.95	2.46	3.0647 (19)	122
C8C—H8CA⋯O1A^v	0.95	2.47	3.078 (2)	122
O2W—H2W1⋯O1D^vi	0.821 (17)	2.114 (18)	2.933 (2)	175 (4)
C8B—H8BA⋯O1D^v	0.95	2.34	3.234 (2)	157
O1C—H1C⋯O3W^v	0.84	1.82	2.651 (2)	168
O2W—H2W2⋯O4Wⁱ	0.828 (17)	1.931 (17)	2.759 (3)	177 (3)

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

Acknowledgments

KS thanks the Department of Chemistry, Mangalore University, for use of their research facilities. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

It is well known that the quinoline ring system is an important structural unit widely existing in alkaloids, therapeutics and synthetic analogues with interesting biological activities (Roma et al. 2000 and Chen et al. 2001). A large variety of quinoline derivatives have been used as antimalarial, anti-inflammatory agents, antiasthmatic, antibacterial, antihypertensive and tyrokinase PDGF-RTK inhibiting agents (Maguire et al. 1994). Furthermore, poly-substituted quinolines have been found to undergo hierarchical self-assembly into a variety of nano- and mesostructures with enhanced electronic and photonic functions (Zhang et al. 2000). The synthesis and structure of Schiff bases have attracted much attention in biology and chemistry (Kahwa et al. 1986). One of the aims of investigating the structural chemistry of Schiff bases is to develop protein and enzyme mimics (Santos et al. 2001). Structural information is useful in investigating the coordination properties of Schiff bases functioning as ligands (Saim et al. 2004). Some Schiff base derivatives were reported to possess antimicrobial, anti-inflammatory and central nervous system activities. Moreover, Schiff bases are also known to have biological activities such as antimicrobial (El-Masry et al.. 2000 & Pandey et al. 1999), antifungal (Singh et al. 1988 & Varma et al. 1986), antitumor (Hodnett et al. 1970; Misra et al. 1981 & Desai et al. 2001), and as herbicides. The crystal structures of Schiff base compounds, viz, bis{4-[(2-hydroxybenzylidine)hydrazino]-8-(trifluoromethyl)quinolinium} sulfate tetrahydrate, (Yathirajan et al. 2007), p-hydroxybenzaldehyde nicotinoylhydrazone monohydrate (Fun et al. 1999), 2-(2-hydroxybenzylidene)-1-(2-picoloyl)hydrazine hemihydrate (Wang et al. 1998), 5-bromo-2-hydroxybenzaldehyde (4-phenyl-1,3-thiazol-2-yl)hydrazone (Sadık et al. 2004) have been reported. A new Schiff base, C₃₄H₃₀F₆N₆O₈S, was synthesized and its crystal structure is reported.

The title compound, C₃₄H₃₀F₆N₆O₈S, crystallizes with four independent cations (A, B, C and D) in the asymmetric unit which is composed of two groups of two cations, one anion and two water molecules [Z'= 2], respectively (Figs. 1–2). The dihedral angle between the mean planes of the 4-hydroxyphenyl and quinolinium groups is 8.9 (7)° in A, 30.1 (6)° in B, 28.8 (8)° in C and 12.8 (1)° in D. Crystal packing is stabilized by intermolecular O—H···O and N—H···O hydrogen bonding between H atoms from 4-hydroxyphenyl oxygen atoms and oxygen atoms from nearby water and sulfate molecules as well as H atoms from the nitrogen atom of the hydrazino group to oxygen atoms from neighboring sulfate molecules linking the molecules into chains with the 4-hydroxyphenyl and quinolimium rings parallel to the [011] plane of the unit cell (Fig. 3). There is also an extensive array of intermolecular hydrogen bonds between water molecules themselves and with sulfate oxygen atoms,in the unit cell as well as hydrogen bond interactions between hydrogen atoms from the hydrazino group and sulfate oxygen atoms. Also, intermolecular π-π stacking interactions occur between adjacent 4-hydroxyphenyl and quinolinium rings as follows: [Cg1, Cg2, Cg3, Cg5, Cg6, Cg9, Cg10, Cg13, Cg14 & Cg15 = center of gravity of (N1A, C5A–C9A), (C1A–C5A, C9A), (C12A–C17A), (N1B, C5B–C9B), (C1B–C5B, C9B), (N1C, C5C–C9C), (C1C–C5C, C9C), (N1C, C5C–C9C), (C1D–C5D, C9D), (C12D–C17D); Cg1···Cg13 = 3.7262 (9) & 3.4140 (9)^ix Å; Cg2···Cg13 = 3.5888 (9)^ix Å; Cg2···Cg14 = 3.9659 (9)^ix Å; Cg3···Cg15 = 3.9401 (10)^ix Å; Cg5···Cg9 = 3.5848 (8)^ix & 3.6314 (9)^x Å; Cg6···Cg9 = 3.8223 (9)^ix & 3.5486 (9)^x Å; Cg6···Cg10 = 3.6649 (9)^xi Å; ix = x, y, z; x = 1/2 - x, 1/2 - y, z; xi = -1/2 + x, 1/2 - y, z].

Experimental

A mixture of 4-hydrazino-8-(trifluoromethyl)quinoline (1.135 g, 0.005 mol) and 4-hydroxybenzaldehyde (0.61 g, 0.005 mol) in 15 ml of absolute alcohol containing 2 drops of sulfuric acid was refluxed for about 3 h. On cooling, the solid separated, was filtered and recrystallized from DMF (m.p.: Above 523 K).