(E)-2-[4-(Dimethyl­amino)styr­yl]-1-methyl­quinolinium iodide sesquihydrate

Chantrapromma, S.; Kobkeatthawin, T.; Chanawanno, K.; Karalai, C.; Fun, H.-K.

doi:10.1107/S1600536808010465

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Pages o876-o877

doi:10.1107/S1600536808010465

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(E)-2-[4-(Dimethylamino)styryl]-1-methylquinolinium iodide sesquihydrate

Suchada Chantrapromma,^a ^* Thawanrat Kobkeatthawin,^a Kullapa Chanawanno,^a Chatchanok Karalai ^a and Hoong-Kun Fun ^b ‡

^aDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand, and ^bX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suchada.c@psu.ac.th

(Received 30 March 2008; accepted 16 April 2008; online 18 April 2008)

In the title compound, C₂₀H₂₁N₂^+.I⁻·1.5H₂O, the cation exists in the E configuration and is not planar. The dihedral angle between the quinolinium and dimethylaminophenyl rings is 9.26 (6)°. The O atom of one of the solvent water molecules lies on a twofold rotation axis. In the crystal structure, the cations form one-dimensional zigzag chains along the [001] direction. The cations are linked to water molecules and iodide ions through weak C—H⋯O and C—H⋯I interactions, respectively. Water molecules and iodide ions form O—H⋯O and O—H⋯I hydrogen bonds, which stabilize the crystal structure. A C—H⋯π interaction is also present.

Related literature

For bond lengths, see: Allen et al. (1987 ). For background to non-linear optical (NLO) materials research, see: Chia et al. (1995 ); Marder et al. (1994 ); Otero et al. (2002 ); Pan et al. (1996 ). For related structures, see for example: Chantrapromma et al. (2006 , 2007a ,b ,c ,d ); Dittrich et al. (2003 ); Jindawong et al. (2005 ); Kobkeatthawin et al. (2008 ); Nogi et al. (2000 ); Sato et al. (1999 ); Umezawa et al. (2000 ).

Experimental

Crystal data

C₂₀H₂₁N₂⁺·I⁻·1.5H₂O
M_r = 443.31
Monoclinic, C 2/c
a = 20.8997 (4) Å
b = 10.5941 (2) Å
c = 18.4020 (4) Å
β = 113.047 (1)°
V = 3749.24 (13) Å³
Z = 8
Mo Kα radiation
μ = 1.72 mm⁻¹
T = 100.0 (1) K
0.52 × 0.35 × 0.12 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.469, T_max = 0.818
50083 measured reflections
8240 independent reflections
7476 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.068
S = 1.07
8240 reflections
237 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.58 e Å⁻³
Δρ_min = −0.80 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯I1ⁱ	0.85 (3)	2.74 (3)	3.5832 (16)	172 (3)
O2W—H1W2⋯O1W	0.83 (3)	2.10 (3)	2.9164 (19)	167 (3)
O1W—H2W1⋯I1ⁱⁱ	0.79 (3)	2.94 (3)	3.7267 (16)	174 (3)
C3—H3A⋯O2Wⁱⁱⁱ	0.93	2.60	3.371 (2)	141
C7—H7A⋯I1^iv	0.93	3.04	3.9290 (18)	161
C17—H17A⋯I1ⁱⁱ	0.93	3.01	3.8784 (14)	157
C2—H2A⋯Cg1ⁱⁱ	0.93	3.02	3.7648 (17)	138
Symmetry codes: (i) $[-x, y, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ . Cg1 is the centroid of the C12–C17 ring.

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808010465/sj2479sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010465/sj2479Isup2.hkl

checkCIF report

Comment top

Organic molecules with large π systems have been extensively used in attempts to obtain non-linear optical (NLO) materials (Chia et al., 1995; Dittrich et al., 2003; Marder et al., 1994; Nogi et al., 2000; Otero et al., 2002; Pan et al., 1996; Sato et al., 1999). We have previously synthesized and crystallized several ionic organic salts of quinolinium derivatives which have a conjugate π system to study their non-linear optical properties (Chantrapromma et al., 2006; 2007a; 2007b; 2007c; 2007d; Jindawong et al., 2005). Previous investigations by Marder et al., 1994, Pan et al., 1996 and Umezawa et al., 2000 reported that 1-methyl-4-(2-(4-(dimethylamino)phenyl)ethenyl)pyridinium p-toluenesulfonate (DAST) is a promising second-order NLO material. Based on this information and our previous investigation (Chantrapromma et al., 2007c), we have designed and synthesized the title compound (I) with the replacement of the 3-hydroxy-4-methoxyphenyl ring in the cation of 2-[(E)-(3-hydroxy-4-methoxyphenyl)ethenyl]-1-methylquinolinium iodide monohydrate which showed second-order NLO properties (Chantrapromma et al., 2007c) by the 4-dimethylaminophenyl ring and its crystal structure was reported here. However since second-order NLO effects are created only when chromophores are arranged in a non-centrosymmetric manner, the title compound, which crystallized in the centrosymmetric space group C2/c, does not exhibit any second-order NLO properties.

The asymmetric unit of the title compound consists of one C₂₀H₂₁N₂⁺ cation, one I^- anion and 1.5 H₂O molecules. The remaining cell contents are generated by symmetry with the O2W atom (symmetry code: -x, y, 1/2 - z) lying on a two-fold rotation axis. The cation exists in the E configuration with respect to the C10═C11 double bond [1.357 (2) Å] and is not planar as indicated by a dihedral angle of 9.26 (6)° between the quinolinium and the dimethylaminophenyl rings. This value is relatively wider than the corresponding angle (3.41 (7)°) reported for the closely related structure of the 4-methoxybenzenesulfonate salt of the same cation (Kobkeatthawin et al., 2008). This may be due to packing effects involving the different counterions. The orientation of the ethenyl unit with respect to the quinolinium and the dimethylaminophenyl rings can be indicated by the torsion angles C8–C9–C10–C11 = 8.5 (2)° and C10–C11–C12–C17 = -1.2 (2)°. The bond lengths and angles are in normal ranges (Allen et al., 1987) and are comparable to those in closely related structures (Chantrapromma et al., 2006; 2007a; 2007b; 2007c; Kobkeatthawin et al., 2008).

In the crystal packing (Fig. 2), the cations form one-dimensional zigzag chains along the [0 0 1] direction. Water molecules contribute to an O2W—H1W2···O1W hydrogen bond. The cations are linked to water molecules and iodide ions through weak C—H···O and C—H···I interactions respectively (Table 1). Water molecules and iodide ions are interconnected by O—H···I hydrogen bonds (O1W—H1W1···I1 and O1W—H2W1···I1 symmetry codes: -x, y, 1/2 - z and x, 1 - y, -1/2 + z, respectively). The crystal is further stabilized by O—H···O and O—H···I hydrogen bonds together with weak C—H···O and C—H···I interactions. A C2—H2A···π interaction to the dimethylaminophenyl ring [C12–C17] was also observed: C2—H2A = 0.93; H2A···Cgⁱ = 3.0219; C2—Cg₁ⁱ = 3.7648 (17) Å; C2—H2A···Cg₁ⁱ = 138°. [Cg₁ⁱ is the centroid of the C12–C17 ring (symmetry code: (i): x, 1 - y, -1/2 + z)].

Related literature top

For bond lengths and angles, see: Allen et al. (1987). For background to non-linear optical (NLO) materials research, see: Chia et al. (1995); Marder et al. (1994); Otero et al. (2002); Pan et al. (1996). For related structures, see for example: Chantrapromma et al. (2006, 2007a,b,c,d); Dittrich et al. (2003); Jindawong et al. (2005); Kobkeatthawin et al. (2008); Nogi et al. (2000); Sato et al. (1999); Umezawa et al. (2000). Cg1 is the

centroid of the C12–C17 ring.

Experimental top

The title compound was synthesized by mixing a 1:1:1 molar ratio solution of 1,2-dimethylquinolinium iodide (2.00 g, 7.01 mmol), dimethylaminobenzaldehyde (1.05 g, 7.01 mmol) and piperidine (0.70 g, 7.01 mmol) in hot methanol (50 ml). The resulting solution was refluxed for 6 h under a nitrogen atmosphere. The resulting solid was filtered off, washed with methanol and recrystallized from methanol to give green crystals. Single crystals of the title compound suitable for x-ray structure determination were recrystalized from methanol/ethanol solvent (1:1 v/v) by slow evaporation of the solvent at room temperature after a few weeks. (Mp. 491–493 K).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The asymmetric unit of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. O2W (symmetry code: -x, y, 1/2 - z) lies on a two-fold rotation axis.
	Fig. 2. The crystal packing of (I) viewed along the a axis, showing the one-dimensional zigzag chains of the cations running along the c direction. The O—H···O and O—H···I hydrogen bonds and weak C—H···O interactions are drawn as dashed lines.

(E)-2-[4-(Dimethylamino)styryl]-1-methylquinolinium iodide sesquihydrate top

Crystal data top

C₂₀H₂₁N₂⁺·I⁻·1.5H₂O	F(000) = 1784
M_r = 443.31	D_x = 1.571 Mg m⁻³
Monoclinic, C2/c	Melting point = 491–493 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 20.8997 (4) Å	Cell parameters from 8240 reflections
b = 10.5941 (2) Å	θ = 2.1–35.0°
c = 18.4020 (4) Å	µ = 1.72 mm⁻¹
β = 113.047 (1)°	T = 100 K
V = 3749.24 (13) Å³	Block, green
Z = 8	0.52 × 0.35 × 0.12 mm

Data collection top

Bruker SMART APEX2 CCD area-detector diffractometer	8240 independent reflections
Radiation source: fine-focus sealed tube	7476 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 8.33 pixels mm^-1	θ_max = 35.0°, θ_min = 2.1°
ω scans	h = −33→33
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −17→15
T_min = 0.469, T_max = 0.818	l = −29→28
50083 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0246P)² + 7.1959P] where P = (F_o² + 2F_c²)/3
8240 reflections	(Δ/σ)_max = 0.001
237 parameters	Δρ_max = 1.58 e Å⁻³
0 restraints	Δρ_min = −0.80 e Å⁻³

Crystal data top

C₂₀H₂₁N₂⁺·I⁻·1.5H₂O	V = 3749.24 (13) Å³
M_r = 443.31	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 20.8997 (4) Å	µ = 1.72 mm⁻¹
b = 10.5941 (2) Å	T = 100 K
c = 18.4020 (4) Å	0.52 × 0.35 × 0.12 mm
β = 113.047 (1)°

Data collection top

Bruker SMART APEX2 CCD area-detector diffractometer	8240 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	7476 reflections with I > 2σ(I)
T_min = 0.469, T_max = 0.818	R_int = 0.032
50083 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 1.58 e Å⁻³
8240 reflections	Δρ_min = −0.80 e Å⁻³
237 parameters

Special details top

Experimental. The low-temparture data was collected with the Oxford Cryosystem Cobra low-temperature attachment.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
I1	0.121463 (5)	0.401312 (10)	0.489877 (6)	0.02205 (3)
N1	0.34849 (6)	0.45765 (12)	−0.04848 (7)	0.0163 (2)
N2	0.16088 (7)	0.23257 (14)	0.29101 (8)	0.0219 (2)
C1	0.39458 (7)	0.47357 (14)	−0.08616 (8)	0.0173 (2)
C2	0.38630 (8)	0.57284 (16)	−0.13994 (9)	0.0222 (3)
H2A	0.3488	0.6279	−0.1525	0.027*
C3	0.43416 (9)	0.58795 (17)	−0.17383 (10)	0.0249 (3)
H3A	0.4283	0.6533	−0.2096	0.030*
C4	0.49123 (8)	0.50731 (18)	−0.15566 (9)	0.0244 (3)
H4A	0.5234	0.5202	−0.1784	0.029*
C5	0.49965 (8)	0.40906 (16)	−0.10418 (9)	0.0219 (3)
H5A	0.5371	0.3542	−0.0929	0.026*
C6	0.45170 (8)	0.39079 (14)	−0.06823 (8)	0.0183 (2)
C7	0.45974 (8)	0.29187 (16)	−0.01383 (9)	0.0211 (3)
H7A	0.4961	0.2347	−0.0029	0.025*
C8	0.41475 (8)	0.27979 (15)	0.02247 (9)	0.0201 (3)
H8A	0.4206	0.2142	0.0581	0.024*
C9	0.35853 (7)	0.36612 (14)	0.00684 (8)	0.0163 (2)
C10	0.31320 (7)	0.35646 (14)	0.04900 (8)	0.0173 (2)
H10A	0.2735	0.4065	0.0326	0.021*
C11	0.32564 (7)	0.27790 (14)	0.11134 (8)	0.0170 (2)
H11A	0.3652	0.2275	0.1265	0.020*
C12	0.28250 (7)	0.26643 (13)	0.15584 (8)	0.0157 (2)
C13	0.29994 (7)	0.18026 (14)	0.21874 (9)	0.0185 (2)
H13A	0.3396	0.1309	0.2309	0.022*
C14	0.26020 (7)	0.16647 (14)	0.26310 (9)	0.0193 (2)
H14A	0.2730	0.1075	0.3038	0.023*
C15	0.20009 (7)	0.24148 (14)	0.24709 (8)	0.0164 (2)
C16	0.18213 (7)	0.32815 (14)	0.18357 (8)	0.0177 (2)
H16A	0.1428	0.3783	0.1714	0.021*
C17	0.22208 (7)	0.33918 (14)	0.13970 (8)	0.0176 (2)
H17A	0.2088	0.3964	0.0981	0.021*
C18	0.17497 (9)	0.13464 (18)	0.35064 (10)	0.0262 (3)
H18A	0.2231	0.1376	0.3857	0.039*
H18B	0.1646	0.0535	0.3254	0.039*
H18C	0.1465	0.1481	0.3801	0.039*
C19	0.09759 (8)	0.30611 (17)	0.27093 (10)	0.0236 (3)
H19A	0.1078	0.3939	0.2680	0.035*
H19B	0.0792	0.2943	0.3107	0.035*
H19C	0.0640	0.2788	0.2208	0.035*
C20	0.28968 (8)	0.54554 (16)	−0.07022 (10)	0.0223 (3)
H20A	0.2575	0.5167	−0.0483	0.034*
H20B	0.2667	0.5494	−0.1267	0.034*
H20C	0.3064	0.6280	−0.0499	0.034*
O1W	0.03830 (8)	0.54957 (15)	0.13362 (8)	0.0297 (3)
O2W	0.0000	0.6809 (2)	0.2500	0.0385 (5)
H1W2	0.0114 (15)	0.633 (3)	0.2215 (16)	0.044 (8)*
H1W1	0.0030 (16)	0.508 (3)	0.1033 (17)	0.049 (8)*
H2W1	0.0580 (16)	0.564 (3)	0.1055 (18)	0.049 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01875 (5)	0.02151 (5)	0.02561 (5)	−0.00453 (3)	0.00840 (4)	−0.00498 (4)
N1	0.0154 (5)	0.0157 (5)	0.0180 (5)	0.0016 (4)	0.0066 (4)	0.0002 (4)
N2	0.0203 (5)	0.0256 (6)	0.0235 (6)	0.0038 (5)	0.0126 (5)	0.0083 (5)
C1	0.0164 (5)	0.0198 (6)	0.0165 (5)	−0.0016 (5)	0.0073 (5)	−0.0020 (5)
C2	0.0190 (6)	0.0242 (7)	0.0236 (6)	0.0016 (5)	0.0086 (5)	0.0041 (5)
C3	0.0233 (7)	0.0289 (8)	0.0229 (7)	−0.0006 (6)	0.0096 (6)	0.0055 (6)
C4	0.0214 (6)	0.0351 (8)	0.0199 (6)	−0.0028 (6)	0.0117 (5)	−0.0010 (6)
C5	0.0180 (6)	0.0282 (7)	0.0205 (6)	0.0022 (5)	0.0088 (5)	−0.0032 (5)
C6	0.0177 (6)	0.0205 (6)	0.0167 (5)	0.0008 (5)	0.0067 (5)	−0.0009 (5)
C7	0.0198 (6)	0.0222 (7)	0.0219 (6)	0.0056 (5)	0.0088 (5)	0.0013 (5)
C8	0.0183 (6)	0.0222 (7)	0.0214 (6)	0.0051 (5)	0.0095 (5)	0.0036 (5)
C9	0.0168 (5)	0.0153 (5)	0.0173 (5)	0.0002 (4)	0.0072 (5)	−0.0001 (4)
C10	0.0182 (6)	0.0172 (6)	0.0185 (6)	−0.0002 (5)	0.0093 (5)	−0.0006 (5)
C11	0.0149 (5)	0.0184 (6)	0.0179 (5)	0.0003 (4)	0.0068 (4)	−0.0001 (5)
C12	0.0149 (5)	0.0160 (5)	0.0162 (5)	−0.0004 (4)	0.0060 (4)	0.0004 (4)
C13	0.0162 (5)	0.0194 (6)	0.0199 (6)	0.0031 (5)	0.0071 (5)	0.0036 (5)
C14	0.0183 (6)	0.0193 (6)	0.0208 (6)	0.0028 (5)	0.0082 (5)	0.0057 (5)
C15	0.0152 (5)	0.0173 (6)	0.0164 (5)	−0.0011 (4)	0.0059 (4)	0.0012 (4)
C16	0.0161 (5)	0.0182 (6)	0.0187 (6)	0.0021 (4)	0.0067 (5)	0.0036 (5)
C17	0.0179 (6)	0.0179 (6)	0.0178 (6)	0.0023 (5)	0.0079 (5)	0.0041 (5)
C18	0.0246 (7)	0.0310 (8)	0.0267 (7)	0.0036 (6)	0.0143 (6)	0.0111 (6)
C19	0.0213 (6)	0.0291 (8)	0.0236 (6)	0.0040 (6)	0.0125 (5)	0.0025 (6)
C20	0.0209 (6)	0.0212 (7)	0.0284 (7)	0.0064 (5)	0.0133 (6)	0.0048 (5)
O1W	0.0271 (6)	0.0340 (7)	0.0266 (6)	0.0012 (5)	0.0092 (5)	0.0014 (5)
O2W	0.0530 (13)	0.0278 (10)	0.0469 (12)	0.000	0.0329 (11)	0.000

Geometric parameters (Å, º) top

N1—C9	1.3614 (19)	C11—C12	1.4411 (19)
N1—C1	1.4001 (18)	C11—H11A	0.9300
N1—C20	1.4672 (19)	C12—C13	1.406 (2)
N2—C15	1.3611 (18)	C12—C17	1.408 (2)
N2—C19	1.453 (2)	C13—C14	1.381 (2)
N2—C18	1.454 (2)	C13—H13A	0.9300
C1—C2	1.408 (2)	C14—C15	1.417 (2)
C1—C6	1.412 (2)	C14—H14A	0.9300
C2—C3	1.380 (2)	C15—C16	1.417 (2)
C2—H2A	0.9300	C16—C17	1.3750 (19)
C3—C4	1.397 (2)	C16—H16A	0.9300
C3—H3A	0.9300	C17—H17A	0.9300
C4—C5	1.372 (2)	C18—H18A	0.9600
C4—H4A	0.9300	C18—H18B	0.9600
C5—C6	1.414 (2)	C18—H18C	0.9600
C5—H5A	0.9300	C19—H19A	0.9600
C6—C7	1.413 (2)	C19—H19B	0.9600
C7—C8	1.356 (2)	C19—H19C	0.9600
C7—H7A	0.9300	C20—H20A	0.9600
C8—C9	1.427 (2)	C20—H20B	0.9600
C8—H8A	0.9300	C20—H20C	0.9600
C9—C10	1.4442 (19)	O1W—H1W1	0.85 (3)
C10—C11	1.357 (2)	O1W—H2W1	0.79 (3)
C10—H10A	0.9300	O2W—H1W2	0.83 (3)

C9—N1—C1	121.43 (12)	C12—C11—H11A	117.4
C9—N1—C20	121.57 (12)	C13—C12—C17	116.83 (12)
C1—N1—C20	116.99 (12)	C13—C12—C11	120.29 (13)
C15—N2—C19	120.78 (13)	C17—C12—C11	122.88 (13)
C15—N2—C18	120.43 (13)	C14—C13—C12	122.22 (13)
C19—N2—C18	118.03 (12)	C14—C13—H13A	118.9
N1—C1—C2	121.28 (13)	C12—C13—H13A	118.9
N1—C1—C6	119.48 (13)	C13—C14—C15	120.47 (13)
C2—C1—C6	119.22 (13)	C13—C14—H14A	119.8
C3—C2—C1	119.55 (15)	C15—C14—H14A	119.8
C3—C2—H2A	120.2	N2—C15—C14	121.92 (13)
C1—C2—H2A	120.2	N2—C15—C16	120.54 (13)
C2—C3—C4	121.53 (15)	C14—C15—C16	117.54 (12)
C2—C3—H3A	119.2	C17—C16—C15	120.92 (13)
C4—C3—H3A	119.2	C17—C16—H16A	119.5
C5—C4—C3	119.73 (14)	C15—C16—H16A	119.5
C5—C4—H4A	120.1	C16—C17—C12	122.01 (13)
C3—C4—H4A	120.1	C16—C17—H17A	119.0
C4—C5—C6	120.29 (14)	C12—C17—H17A	119.0
C4—C5—H5A	119.9	N2—C18—H18A	109.5
C6—C5—H5A	119.9	N2—C18—H18B	109.5
C1—C6—C7	118.76 (13)	H18A—C18—H18B	109.5
C1—C6—C5	119.66 (14)	N2—C18—H18C	109.5
C7—C6—C5	121.58 (14)	H18A—C18—H18C	109.5
C8—C7—C6	120.39 (14)	H18B—C18—H18C	109.5
C8—C7—H7A	119.8	N2—C19—H19A	109.5
C6—C7—H7A	119.8	N2—C19—H19B	109.5
C7—C8—C9	121.03 (14)	H19A—C19—H19B	109.5
C7—C8—H8A	119.5	N2—C19—H19C	109.5
C9—C8—H8A	119.5	H19A—C19—H19C	109.5
N1—C9—C8	118.76 (13)	H19B—C19—H19C	109.5
N1—C9—C10	120.71 (13)	N1—C20—H20A	109.5
C8—C9—C10	120.53 (13)	N1—C20—H20B	109.5
C11—C10—C9	123.26 (13)	H20A—C20—H20B	109.5
C11—C10—H10A	118.4	N1—C20—H20C	109.5
C9—C10—H10A	118.4	H20A—C20—H20C	109.5
C10—C11—C12	125.20 (13)	H20B—C20—H20C	109.5
C10—C11—H11A	117.4	H1W1—O1W—H2W1	102 (3)

C9—N1—C1—C2	−176.27 (14)	C7—C8—C9—N1	3.4 (2)
C20—N1—C1—C2	2.6 (2)	C7—C8—C9—C10	−176.63 (14)
C9—N1—C1—C6	1.9 (2)	N1—C9—C10—C11	−171.48 (14)
C20—N1—C1—C6	−179.27 (14)	C8—C9—C10—C11	8.5 (2)
N1—C1—C2—C3	177.80 (15)	C9—C10—C11—C12	179.05 (14)
C6—C1—C2—C3	−0.3 (2)	C10—C11—C12—C13	179.02 (14)
C1—C2—C3—C4	−0.4 (3)	C10—C11—C12—C17	−1.2 (2)
C2—C3—C4—C5	1.3 (3)	C17—C12—C13—C14	0.0 (2)
C3—C4—C5—C6	−1.4 (2)	C11—C12—C13—C14	179.79 (14)
N1—C1—C6—C7	1.5 (2)	C12—C13—C14—C15	−1.0 (2)
C2—C1—C6—C7	179.65 (14)	C19—N2—C15—C14	−176.95 (15)
N1—C1—C6—C5	−177.92 (13)	C18—N2—C15—C14	−7.2 (2)
C2—C1—C6—C5	0.2 (2)	C19—N2—C15—C16	3.7 (2)
C4—C5—C6—C1	0.6 (2)	C18—N2—C15—C16	173.45 (15)
C4—C5—C6—C7	−178.79 (15)	C13—C14—C15—N2	−178.22 (15)
C1—C6—C7—C8	−2.3 (2)	C13—C14—C15—C16	1.2 (2)
C5—C6—C7—C8	177.06 (15)	N2—C15—C16—C17	178.95 (15)
C6—C7—C8—C9	−0.1 (2)	C14—C15—C16—C17	−0.5 (2)
C1—N1—C9—C8	−4.2 (2)	C15—C16—C17—C12	−0.5 (2)
C20—N1—C9—C8	176.94 (14)	C13—C12—C17—C16	0.7 (2)
C1—N1—C9—C10	175.76 (13)	C11—C12—C17—C16	−179.05 (14)
C20—N1—C9—C10	−3.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···I1ⁱ	0.85 (3)	2.74 (3)	3.5832 (16)	172 (3)
O2W—H1W2···O1W	0.83 (3)	2.10 (3)	2.9164 (19)	167 (3)
O1W—H2W1···I1ⁱⁱ	0.79 (3)	2.94 (3)	3.7267 (16)	174 (3)
C3—H3A···O2Wⁱⁱⁱ	0.93	2.60	3.371 (2)	141
C7—H7A···I1^iv	0.93	3.04	3.9290 (18)	161
C17—H17A···I1ⁱⁱ	0.93	3.01	3.8784 (14)	157
C2—H2A···Cg1ⁱⁱ	0.93	3.02	3.7648 (17)	138

Symmetry codes: (i) −x, y, −z+1/2; (ii) x, −y+1, z−1/2; (iii) −x+1/2, −y+3/2, −z; (iv) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₁N₂⁺·I⁻·1.5H₂O
M_r	443.31
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	100
a, b, c (Å)	20.8997 (4), 10.5941 (2), 18.4020 (4)
β (°)	113.047 (1)
V (Å³)	3749.24 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.72
Crystal size (mm)	0.52 × 0.35 × 0.12

Data collection
Diffractometer	Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.469, 0.818
No. of measured, independent and observed [I > 2σ(I)] reflections	50083, 8240, 7476
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.068, 1.07
No. of reflections	8240
No. of parameters	237
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.58, −0.80

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···I1ⁱ	0.85 (3)	2.74 (3)	3.5832 (16)	172 (3)
O2W—H1W2···O1W	0.83 (3)	2.10 (3)	2.9164 (19)	167 (3)
O1W—H2W1···I1ⁱⁱ	0.79 (3)	2.94 (3)	3.7267 (16)	174 (3)
C3—H3A···O2Wⁱⁱⁱ	0.93	2.5992	3.371 (2)	141
C7—H7A···I1^iv	0.93	3.0383	3.9290 (18)	161
C17—H17A···I1ⁱⁱ	0.93	3.0074	3.8784 (14)	157
C2—H2A···Cg1ⁱⁱ	0.93	3.0219	3.7648 (17)	138

Symmetry codes: (i) −x, y, −z+1/2; (ii) x, −y+1, z−1/2; (iii) −x+1/2, −y+3/2, −z; (iv) x+1/2, −y+1/2, z−1/2.

Footnotes

‡Additional correspondence author, e-mail: hkfun@usm.my.

Acknowledgements

The authors thank the Prince of Songkla University for financial support. The authors also thank the Malaysian Government and Universiti Sains Malaysia for Research University Golden Goose grant No. 1001/PFIZIK/811012.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–S19. CrossRef Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chantrapromma, S., Jindawong, B., Fun, H.-K. & Patil, P. S. (2007a). Anal. Sci. 23, x81–x82. Google Scholar
Chantrapromma, S., Jindawong, B., Fun, H.-K. & Patil, P. S. (2007b). Acta Cryst. E63, o2124–o2126. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Jindawong, B., Fun, H.-K. & Patil, P. S. (2007c). Acta Cryst. E63, o2321–o2323. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Jindawong, B., Fun, H.-K., Patil, P. S. & Karalai, C. (2006). Acta Cryst. E62, o1802–o1804. Web of Science CSD CrossRef IUCr Journals Google Scholar
Chantrapromma, S., Jindawong, B., Fun, H.-K., Patil, P. S. & Karalai, C. (2007d). Anal. Sci. 23, x27–x28. CAS Google Scholar
Chia, W.-L., Chen, C.-N. & Sheu, H.-J. (1995). Mater. Res. Bull. 30, 1421–1430. CrossRef CAS Web of Science Google Scholar
Dittrich, Ph., Bartlome, R., Montemezzani, G. & Günter, P. (2003). Appl. Surf. Sci. 220, 88–95. Web of Science CrossRef CAS Google Scholar
Jindawong, B., Chantrapromma, S., Fun, H.-K. & Karalai, C. (2005). Acta Cryst. E61, o3237–o3239. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kobkeatthawin, T., Ruanwas, P., Chantrapromma, S. & Fun, H.-K. (2008). Acta Cryst. E64, o642–o643. Web of Science CSD CrossRef IUCr Journals Google Scholar
Marder, S. R., Perry, J. W. & Yakymyhyn, C. P. (1994). Chem. Mater. 6, 1137–1147. CSD CrossRef CAS Web of Science Google Scholar
Nogi, K., Anwar, U., Tsuji, K., Duan, X.-M., Okada, S., Oikawa, H., Matsuda, H. & Nakanishi, H. (2000). Nonlinear Optics, 24, 35–40. CAS Google Scholar
Otero, M., Herranz, M. A., Seoane, C., Martín, N., Garín, J., Orduna, J., Alcalá, R. & Villacampa, B. (2002). Tetrahedron. 58, 7463–7475. Web of Science CrossRef CAS Google Scholar
Pan, F., Knöpfle, G., Bosshard, Ch., Follonier, S., Spreiter, R., Wong, M. S. & Günter, P. (1996). Appl. Phys. Lett. 69, 13–15. CrossRef CAS Web of Science Google Scholar
Sato, N., Rikukawa, M., Sanui, K. & Ogata, N. (1999). Synth. Met. 101, 132–133. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Umezawa, H., Tsuji, K., Usman, A., Duan, X.-M., Okada, S., Oikawa, H. & Matsuda, H. (2000). Nonlinear Optics, 24, 73–78. CAS Google Scholar