Bis[(E)-2-(3-hydr­oxy-4-methoxy­phen­yl)ethen­yl]-1-methyl­quinolinium tetra­iodidozincate(II) methanol solvate

Suchada Chantrapromma; Hoong-Kun Fun; Kullapa Chanawanno; Pumsak Ruanwas

doi:10.1107/S1600536807064215

. 2007 Dec 6;64(Pt 1):m126–m127. doi: 10.1107/S1600536807064215

Bis[(E)-2-(3-hydroxy-4-methoxyphenyl)ethenyl]-1-methylquinolinium tetraiodidozincate(II) methanol solvate¹

Suchada Chantrapromma ^a,^‡, Hoong-Kun Fun ^b,^*, Kullapa Chanawanno ^a, Pumsak Ruanwas ^a

PMCID: PMC2915076 PMID: 21200484

Abstract

In the title compound, (C₁₉H₁₈NO₂)₂[ZnI₄]·CH₃OH, each cation is nearly planar and exists in an E configuration, the dihedral angles between the quinolinium systems and the benzene rings being 1.78 (10) and 5.44 (10)° for the two cations. The [ZnI₄]²⁻ anion displays a very slightly distorted tetrahedral geometry. There are intramolecular O—H⋯O hydrogen bonds between the hydroxy and methoxy groups in each cation which generate S(5) ring motifs. In the crystal structure, cations are linked together by O—H⋯O hydrogen bonds and weak C—H⋯O interactions, whereas the anions are linked to the cations through weak C—H⋯I interactions. The asymmetric unit also contains a methanol solvent molecule which is linked to one of the cations by an O—H⋯O hydrogen bond and the anion through an O—H⋯I hydrogen bond. The crystal is further stabilized by C—H⋯π and π–π interactions [centroid–centroid distances 3.6054 (15) and 3.6057 (15) Å].

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see for example: Chantrapromma et al. (2006a ▶,b ▶; 2007a ▶,b ▶,c ▶); Fun et al. (2006 ▶); Glavcheva et al. (2004 ▶); Jindawong et al. (2005 ▶). For background to non-linear optics, see for example: Oudar & Chemla (1977 ▶); Williams (1984 ▶).

Experimental

Crystal data

(C₁₉H₁₈NO₂)₂[ZnI₄]·CH₄O
M _r = 1189.72
Monoclinic,
a = 8.6449 (1) Å
b = 23.4312 (4) Å
c = 19.7763 (3) Å
β = 91.724 (1)°
V = 4004.08 (10) Å³
Z = 4
Mo Kα radiation
μ = 3.74 mm⁻¹
T = 100.0 (1) K
0.43 × 0.28 × 0.13 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.295, T _max = 0.646
100181 measured reflections
18959 independent reflections
15305 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.091
S = 1.10
18959 reflections
465 parameters
H-atom parameters constrained
Δρ_max = 4.98 e Å⁻³
Δρ_min = −1.46 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 1998 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807064215/sj2450sup1.cif

e-64-0m126-sup1.cif^{(30.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807064215/sj2450Isup2.hkl

e-64-0m126-Isup2.hkl^{(926.5KB, 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
O1—H1O1⋯O2	0.82	2.15	2.611 (3)	116
O3—H1O3⋯O4	0.82	2.23	2.673 (3)	114
O3—H1O3⋯O5ⁱ	0.82	1.92	2.693 (3)	156
O5—H1O5⋯I1ⁱⁱ	0.82	2.82	3.6161 (17)	163
C2—H2A⋯O3ⁱⁱⁱ	0.93	2.56	3.476 (3)	167
C18—H18B⋯O3ⁱⁱⁱ	0.96	2.60	3.355 (3)	136
C27—H27A⋯I4^iv	0.93	3.02	3.899 (3)	158
C19—H19B⋯Cg4	0.96	2.99	3.944 (3)	172
C38—H38B⋯Cg2	0.96	2.94	3.871 (3)	165

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg2 and Cg4 are the centroids of the C12–C17 and C31–C36 benzene rings, respectively.

Acknowledgments

The authors thank Prince of Songkla University for a research grant. The authors also thank the Malaysian Government and Universiti Sains Malaysia for the Scientific Advancement Grant Allocation (SAGA) grant No. 304/PFIZIK/653003/A118. KC thanks the Development and Promotion of Science and Technology Talents Project for a study grant. PR thanks the Graduate School, Prince of Songkla University.

supplementary crystallographic information

Comment

There is considerable interest in the synthesis of new materials with large second-order nonlinear properties because of their potential usage in a varity of applications such as in optical data storage, optical information processing and telecommunication. We have previously reported the structures of several quinolinium salts (Chantrapromma et al., 2006a,b, 2007a,b,c; Fun et al., 2006; Jindawong et al., 2005), which were synthesized to study their nonlinear optical (NLO) properties. At the molecular level, a generally popular approach towards NLO materials is to design and systhesize compounds with extended conjugated π systems with donor and acceptor groups because such compounds are likely to exhibit large values of molecular hyperpolarizability (β) and to possess polarizable electrons (as in a conjugated π system) spread over a large distance (Oudar & Chemla, 1977). Quinolinium derivatives are considered to be good conjugated π systems. Organic–inorganic hybrid complexes also present a promising new type of materials for various applications. Thus, we extended our synthesis to this class of materials. This single-crystal X-ray structural study of the title compound was carried out in order to obtain detailed information about its crystal structure. However, the title compound crystallized in the centrosymmetric monoclinic space group P2₁/c and therefore does not exhibit nonlinear optical properties (Williams, 1984).

The asymmetric unit of the title compound consists of two C₁₉H₁₈NO₂⁺ cations, a ZnI₄^2- anion and a methanol solvate molecule (Fig. 1). Each cation is nearly planar as indicated by the dihedral angle between the quinolinium planes and the benzene rings in each cation being 1.78 (10) and 5.44 (10)°, respectively. The H atoms attached to the alkene C atoms C10 and C11 and C29 and C30 are mutually trans; torsion angles C9—C10—C11—C12 = 179.1 (2)° and C28—C29—C30—C31 = -179.3 (2)°. Both the hydroxy and methoxy groups are reasonably coplanar with the benzene rings to which they are attached with torsion angles C19—O2—C15—C16 = -0.4 (4)° and C38—O4—C34—C35 = 1.2 (4)°. Both cations form intramolecular O—H···O hydrogen bonds between the hydroxy and methoxy groups which generate S(5) ring motifs (Bernstein et al., 1995). The two cations are approximately parallel to one another with dihedral angles 7.55 (7)° between the two quinolinium planes (C1–C9/N1 and C20–C28/N2) and 12.82 (12)° between the two benzene rings (C12–C17 and C31–C36). The ZnI₄^2- anion shows only small distortions from a regular tetrahedron as was found previously (Glavcheva et al., 2004). Zn—I bond distances are in the range 2.6035 (3)–2.6409 (3) Å, and I—Zn—I bond angles lie in the range 106.583 (11)–114.187 (11)°. Bond distances and angles of the cations show normal values (Allen et al., 1987) and are comparable with closely related structures (Chantrapromma et al., 2006a,b, 2007a,b,c; Fun et al., 2006; Jindawong et al., 2005).

In the crystal packing, the cations are linked together through O—H···O hydrogen bonds and weak C—H···O interactions (Table 1). The cations are also linked to the ZnI₄^2- anions through weak C27—H27A···I4 interactions (symmetry code: -1 + x, y, -1 + z). The methanol molecule links with the cation by an O3—H1O3···O5 hydrogen bond (symmetry code: 1 - x, -1/2 + y, 1/2 - z) and with the ZnI₄^2- anion by an O5—H1O5···I1 hydrogen bond (symmetry code: 1 - x, 1 - y, 1 - z). The cations are arranged in an antiparallel manner and stacked along the a axis in such a way that the centroid–centroid distance between the C1–C6 (Cg₁) and C12–C17 (Cg₂) rings is 3.6054 (15)Å (symmetry code: 1 - x, 1 - y, 1 - z) and that between the C20–C25 (Cg₃) and C31–C36 (Cg₄) rings is 3.6057 (15)Å (symmetry code: 1 - x, 1 - y, -z), indicating π–π interactions. The crystal is further stabilized by C—H···π interactions (Table 1); Cg₂ and Cg₄ are the centroids of the C12–C17 and C31–C36 benzene rings, respectively.

Experimental

The title compound was synthesized by mixing a solution of 2-[(E)-2-(3-Hydroxy-4-methoxyphenyl)ethynyl]-1-methylquinolinium iodide (Chantrapromma et al., 2006a) (0.20 g, 0.48 mmol) in hot methanol (50 ml) and a solution of ZnI₂ (0.19 g, 0.48 mmol) in hot methanol (30 ml). The mixture was stirred for half an hour and then left at room-temperature. The title compound formed as a red solid after 2 days. Red plates suitable for X-ray diffraction analysis were obtained by recrystallization from a methanol/ethanol (1:2 v/v) by slow evaporation of the solvents at ambient temperature after several days, M.p. 493–494 K.