trans-4-[(4-Dimethyl­amino­phenyl)ethenyl]-N-methyl­quinolinium p-toluene­sulfonate monohydrate

Coe, B.J.; Hall, J.J.; Harris, J.A.; Brunschwig, B.S.; Coles, S.J.; Hursthouse, M.B.

doi:10.1107/S1600536805002138

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 2| February 2005| Pages o464-o467

https://doi.org/10.1107/S1600536805002138

trans-4-[(4-Dimethylaminophenyl)ethenyl]-N-methylquinolinium p-toluenesulfonate monohydrate

Benjamin J. Coe,^a ^* Jonathan J. Hall,^a James A. Harris,^a Bruce S. Brunschwig,^b Simon J. Coles ^c and Michael B. Hursthouse ^c

^aSchool of Chemistry, University of Manchester, Manchester M13 9PL, England, ^bMolecular Materials Research Center, Beckman Institute, MC 139-74, California Institute of Technology, 1200 East California Blvd, Pasadena, CA 91125, USA, and ^cEPSRC National Crystallography Service, School of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, England
^*Correspondence e-mail: b.coe@man.ac.uk

(Received 14 January 2005; accepted 20 January 2005; online 29 January 2005)

In the title salt, C₂₀H₂₁N $[{}_{2}^{+}]$ ·C₇H₇SO $[{}_{3}^{- }]$ ·H₂O, the quinolinium cation exhibits a large molecular non-linear optical (NLO) response, as determined by Stark spectroscopy, but crystallization in the centrosymmetric space group P $[\overline{1}]$ precludes significant bulk NLO effects. Intermolecular O—H⋯O and weak C—H⋯O hydrogen bonding links the constituent molecules into a three-dimensional network.

Comment

The synthesis and study of molecular compounds with non-linear optical (NLO) properties has attracted much attention, because such materials hold promise for applications in optoelectronic and photonic devices (Bosshard et al., 1995 ; Nalwa & Miyata, 1997 ). In order to create efficient quadratic (second-order) NLO materials, both the molecular and bulk properties must be optimized. The majority of promising compounds constitute dipolar donor–π-acceptor (D–π-A) molecules and these must be arranged noncentrosymmetrically in order to afford macroscopic structures capable of showing bulk quadratic NLO effects, such as frequency doubling (second-harmonic generation, SHG).

Within the diverse range of existing NLO compounds, stilbazolium salts are particularly attractive for device applications (Lee & Kim, 1999 ). The archetypal compound trans-4′-(dimethylamino)-N-methyl-4-stilbazolium para-toluenesulfonate (DAST) displays very marked bulk quadratic NLO activity, as originally shown by powder SHG studies (Marder et al., 1989 , 1994 ). At the molecular level, quadratic NLO effects are determined by first hyperpolarizabilities β, and static (`off-resonance') first hyperpolarizabilities β₀ are normally used when comparing active compounds. Hyper-Rayleigh scattering experiments with DAST using a 1064 nm laser yielded a large β₀ value of 364 × 10⁻³⁰ esu (Duan et al., 1995 ). DAST has therefore been intensively investigated over recent years (Meier et al., 2000 ; Kaino et al., 2002 ), including the growth of large high-quality single crystals (Pan et al., 1996 ; Sohma et al., 1999 ; Mohan Kumar et al., 2003 ), and the demonstration of prototype NLO devices for parametric interactions and electro-optical modulation (Meier et al. 1998 ; Bhowmik et al. 2000 ; Geis et al. 2004 ; Taniuchi et al. 2004 ).

In addition to their NLO properties, D–π-A molecules display intense low-energy absorption bands which arise from π(D) → π*(A) intramolecular charge-transfer (ICT) excitations. A two-state model (Oudar & Chemla, 1977 ; Zyss & Oudar, 1982 ) shows that β₀ is proportional to the product of the square of the ICT transition dipole moment μ₁₂ and the dipole moment change Δμ₁₂, and inversely proportional to the square of the ICT energy E_max. Therefore, β₀ increases with increasing intensity and decreasing energy of the ICT absorption. The ICT band of the PF₆^- salt of the cation in (I) ([DAQ⁺]PF₆^-) is red-shifted by ca 0.34 eV, but is ca 85% as intense, when compared with that of the PF₆^- salt of the chromophore in DAST ([DAS⁺]PF₆^-; λ_max = 470 nm, ∊ = 42 800 M⁻¹ dm³ in acetonitrile; Coe et al., 2002 ). This marked red-shifting suggests that the β₀ value of (I) may be larger than that of DAST. We have previously determined β₀ for [DAS⁺]PF₆^- using Stark (electroabsorption) spectroscopy (Coe et al., 2003 ), and have now applied the same approach to [DAQ⁺]PF₆^-. By applying the two-state equation β₀ = 3Δμ₁₂(μ₁₂)²/(E_max)² to data obtained from butyronitrile glasses at 77 K, the results are 236 and 255 × 10⁻³⁰ esu for [DAS⁺]PF₆^- and [DAQ⁺]PF₆^-, respectively. The lower-than-expected increase in β₀ is attributable to a decrease in Δμ₁₂ from 16.3 to 13.3 D on moving from [DAS⁺]PF₆^- to [DAQ⁺]PF₆^-, whilst μ₁₂ remains constant at 9.1 D.

The molecular structure of the cation in (I) is as indicated by ¹H NMR spectroscopy, and similar to that observed previously in the corresponding hexamolybdate salt (Xu et al., 1995 ), although the precision of the present structure is rather higher. The conjugated aromatic system is essentially planar, with a maximum deviation from the mean plane of 0.094 Å for atom C24, and this plane forms an angle of 77.48 (6) ° with the benzene ring plane of the tosylate anion.

The crystal packing structure of (I) is critical in relation to quadratic NLO properties. DAST crystallizes noncentrosymmetrically in the space group Cc (Marder et al., 1989), but unfortunately (I) adopts the centrosymmetric space group P $[\overline{1}]$ and is hence not suitable for bulk NLO effects. Perhaps not unexpectedly, replacement of the pyridinium ring in DAST with a quinolinium group changes the crystallization behaviour. In fact, the presence of water molecules within the crystal structure of (I) leads to a network of hydrogen bonds involving water, the tosylate anion and the chromophoric cation. The water molecules and tosylate anions form centrosymmetric O—H⋯O hydrogen-bonded rings, and weak intermolecular C—H⋯O hydrogen bonds link these rings to the quinolinium moieties to form a three-dimensional network (Fig. 2).

It has been proposed that the natural tendency towards antiparallel dipole aligment between the cations in DAST is overcome by the presence of the intervening tosylate anions (Marder et al., 1989, 1994), but such an effect is not evident in (I). Although this outcome is rather disappointing, salts of the cation in (I) with other anions may well adopt different crystal structures capable of showing bulk NLO behaviour.

Figure 1
A representation of the molecular structure of (I)

, with 50% probability displacement ellipsoids.

Figure 2
A representation of the hydrogen-bonding interactions (dashed lines) in (I)

Experimental

The compound trans-4-[(4-dimethylaminophenyl)-2-ethenyl]-N-methylquinolinium iodide (Bahner et al., 1951 ) was synthesized by adapting a method which has been applied previously to the analogous dibutylamine compound (Alain et al., 2000 ). Piperidine (3 drops) was added to a solution of 4-methyl-N-methylquinolinium iodide (276 mg, 0.968 mmol) and 4-(dimethylamino)benzaldehyde (289 mg, 1.937 mmol) in methanol (20 ml). The solution immediately turned purple and was stirred under reflux for 4 h. After cooling to room temperature, the solution was added dropwise to diethyl ether to afford a dark precipitate which was filtered off, washed with diethyl ether and then water, and dried under vacuum (yield 349 mg, 87%). A portion of this crude material (125 mg, 0.300 mmol) was metathesized to (I) by precipitation from water–aqueous sodium para-toluenesulfonate (yield 115 mg, 83%). Compound (I) has been reported previously (Metzger et al., 1969 ). Crystals of (I) suitable for single-crystal X-ray diffraction measurements were obtained by slow diffusion of diethyl ether vapour into a methanol solution of (I) at room temperature; note that the same method is used to produce SHG-active crystals of DAST (Marder et al., 1994). Analysis, found: C 67.99, H 6.35, N 5.86, S 6.69%; calculated for C₂₇H₂₈N₂O₃S·H₂O: C 67.76, H 6.32, N 5.85, S 6.70%. For spectroscopic studies, a portion of the crude iodide salt was also metathesized to the hexafluorophosphate (previously unreported, to our knowledge) by precipitation from water–aqueous ammonium hexafluorophosphate. Analysis, found: C 55.19, H 4.63, N 6.33%, calculated for C₂₀H₂₁F₆N₂P: C 55.30, H 4.87, N 6.45%. Spectroscopic analysis: ¹H NMR (200 MHz, CD₃COCD₃, δ, p.p.m.): 9.12 (1H, d, J = 6.8 Hz, C₅H₂N), 9.02 (1H, d, J = 8.5 Hz, C₆H₄), 8.46 (1H, d, J = 8.4 Hz, C₆H₄), 8.38 (1H, d, J = 6.6 Hz, C₅H₂N), 8.27 (1H, t, J = 7.9 Hz, C₆H₄), 8.21 (1H, d, J = 15.7 Hz, CH), 8.08 (1H, d, J = 16.2 Hz, CH), 8.03 (1H, t, J = 7.7 Hz, C₆H₄), 7.86 (2H, d, J = 9.0 Hz, C₆H₄—NMe₂), 6.86 (2H, d, J = 9.1 Hz, C₆H₄—NMe₂), 4.68 (3H, s, Me), 3.13 (6H, s, NMe₂); λ_max (nm) [∊ (M⁻¹ dm³)] (MeCN): 540 (36 700), 306 (12 400), 242 (17 900).

Crystal data

C₂₀H₂₁N $[{}_{2}^{+}]$ ·C₇H₇O₃S⁻·H₂O
M_r = 478.59
Triclinic, $[P \overline 1]$
a = 8.033 (4) Å
b = 10.550 (7) Å
c = 14.662 (9) Å
α = 97.75 (7)°
β = 97.87 (4)°
γ = 103.97 (5)°
V = 1176.2 (12) Å³
Z = 2
D_x = 1.351 Mg m⁻³
Mo Kα radiation
Cell parameters from 4905 reflections
θ = 2.9–27.5°
μ = 0.18 mm⁻¹
T = 120 (2) K
Slab, dark green
0.6 × 0.4 × 0.14 mm

Data collection

Bruker-Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.902, T_max = 0.976
22 326 measured reflections
5337 independent reflections
4160 reflections with I > 2σ(I)
R_int = 0.041
θ_max = 27.5°
h = −10 → 10
k = −13 → 13
l = −19 → 18

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.126
S = 1.02
5337 reflections
320 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0684P)² + 0.4268P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.047
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.53 e Å⁻³
Extinction correction: SHELXL97 (Sheldrick, 1997 )
Extinction coefficient: 0.016 (4)

Table 1
Selected geometric parameters (Å, °)

C8—N1	1.453 (3)
C9—N1	1.444 (3)
C10—N1	1.368 (2)
C10—C11	1.400 (3)
C10—C15	1.413 (3)
C11—C12	1.379 (3)
C12—C13	1.399 (2)
C13—C14	1.404 (3)
C13—C16	1.447 (2)
C14—C15	1.375 (2)
C16—C17	1.348 (2)
C17—C18	1.447 (2)
C18—C19	1.390 (2)
C18—C22	1.433 (2)
C19—C20	1.372 (2)
C20—N2	1.328 (2)
C21—N2	1.473 (2)
C22—C27	1.414 (2)
C22—C23	1.418 (2)
C23—N2	1.379 (2)
C23—C24	1.405 (2)
C24—C25	1.366 (2)
C25—C26	1.398 (3)
C26—C27	1.365 (2)

N1—C10—C11	120.83 (17)
N1—C10—C15	121.65 (17)
C11—C10—C15	117.51 (16)
C12—C11—C10	120.62 (17)
C11—C12—C13	122.12 (17)
C12—C13—C14	117.18 (15)
C12—C13—C16	119.35 (16)
C14—C13—C16	123.45 (16)
C15—C14—C13	121.21 (16)
C14—C15—C10	121.29 (17)
C17—C16—C13	127.15 (15)
C16—C17—C18	124.17 (15)
C19—C18—C22	116.75 (15)
C19—C18—C17	121.72 (15)
C22—C18—C17	121.53 (14)
C20—C19—C18	120.79 (16)
N2—C20—C19	122.84 (15)
C27—C22—C23	117.05 (15)
C27—C22—C18	122.72 (14)
C23—C22—C18	120.21 (14)
N2—C23—C24	120.25 (14)
N2—C23—C22	118.87 (15)
C24—C23—C22	120.87 (15)
C25—C24—C23	119.84 (15)
C24—C25—C26	120.22 (16)
C27—C26—C25	120.68 (15)
C26—C27—C22	121.24 (15)
C10—N1—C9	121.38 (17)
C10—N1—C8	120.21 (18)
C9—N1—C8	117.97 (17)
C20—N2—C23	120.50 (14)
C20—N2—C21	118.80 (14)
C23—N2—C21	120.61 (14)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H2O⋯O1ⁱ	0.86 (2)	2.07 (2)	2.922 (3)	175 (2)
O4—H10⋯O2	0.89 (2)	1.95 (3)	2.838 (3)	169 (2)
C14—H14⋯O3	0.95	2.41	3.359 (3)	174
C17—H17⋯O3	0.95	2.49	3.435 (3)	175
C27—H27⋯O3	0.95	2.34	3.282 (3)	172
C3—H3⋯O2ⁱⁱ	0.95	2.59	3.535 (3)	171
C20—H20⋯O1ⁱⁱⁱ	0.95	2.37	3.290 (3)	162
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z; (iii) x+1, y+1, z.

The H atoms of the water molecule were refined independently with isotropic displacement parameters. H atoms bonded to C atoms were placed in calculated positions, with C—H distances of 0.95 Å [0.98 Å for methyl], and included in the refinement in a riding-model approximation, with U_iso = 1.2U_eq(C), or 1.5U_eq(C) for methyl groups.

Data collection: DENZO (Otwinowski & Minor, 1997 ) and COLLECT (Hooft, 1998 ); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805002138/lh6354sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805002138/lh6354Isup2.hkl

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: Please provide missing details.

trans-4-[(4-Dimethylaminophenyl)ethenyl]-N-methylquinolinium p-toluenesulfonate monohydrate top

Crystal data top

C₂₀H₂₁N₂⁺·C₇H₇O₃S⁻·H₂O	Z = 2
M_r = 478.59	F(000) = 508
Triclinic, P1	D_x = 1.351 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.033 (4) Å	Cell parameters from 4905 reflections
b = 10.550 (7) Å	θ = 2.9–27.5°
c = 14.662 (9) Å	µ = 0.18 mm⁻¹
α = 97.75 (7)°	T = 120 K
β = 97.87 (4)°	Slab, dark green
γ = 103.97 (5)°	0.6 × 0.4 × 0.14 mm
V = 1176.2 (12) Å³

Data collection top

Bruker-Nonius KappaCCD area-detector diffractometer	4160 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
φ and ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
T_min = 0.902, T_max = 0.976	k = −13→13
22326 measured reflections	l = −19→18
5337 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0684P)² + 0.4268P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.047
5337 reflections	Δρ_max = 0.28 e Å⁻³
320 parameters	Δρ_min = −0.53 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.016 (4)

Special details top

Experimental. The Tmin and Tmax values reported are those calculated from the SHELX SIZE command. The ratio of experimental transmission factors from SADABS is 0.724295.

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
C1	0.1870 (2)	0.49093 (15)	0.22545 (11)	0.0239 (3)
C2	0.0344 (2)	0.50065 (17)	0.25634 (12)	0.0289 (4)
H2	0.0382	0.538	0.3195	0.035*
C3	−0.1235 (2)	0.45625 (18)	0.19555 (13)	0.0323 (4)
H3	−0.2272	0.4648	0.2171	0.039*
C4	−0.1321 (2)	0.39965 (18)	0.10393 (13)	0.0345 (4)
C5	0.0215 (3)	0.3901 (2)	0.07428 (13)	0.0433 (5)
H5	0.0175	0.3516	0.0113	0.052*
C6	0.1807 (2)	0.4353 (2)	0.13394 (12)	0.0363 (4)
H6	0.2846	0.4281	0.1121	0.044*
C7	−0.3049 (3)	0.3485 (2)	0.03880 (16)	0.0515 (6)
H7A	−0.383	0.2823	0.0653	0.077*
H7B	−0.2874	0.3076	−0.022	0.077*
H7C	−0.3567	0.4222	0.0307	0.077*
C8	−0.2581 (3)	1.0018 (3)	0.06957 (14)	0.0482 (5)
H8A	−0.2393	1.083	0.1152	0.072*
H8B	−0.3833	0.9591	0.0516	0.072*
H8C	−0.2099	1.0239	0.0141	0.072*
C9	−0.2729 (2)	0.7774 (2)	0.10750 (15)	0.0456 (5)
H9A	−0.2615	0.721	0.0511	0.068*
H9B	−0.3956	0.7759	0.1061	0.068*
H9C	−0.2302	0.7441	0.163	0.068*
C10	0.0046 (2)	0.94966 (19)	0.14200 (11)	0.0309 (4)
C11	0.0997 (2)	1.08193 (19)	0.15017 (12)	0.0325 (4)
H11	0.0428	1.1451	0.1301	0.039*
C12	0.2753 (2)	1.12140 (18)	0.18701 (12)	0.0297 (4)
H12	0.3365	1.212	0.1925	0.036*
C13	0.3662 (2)	1.03238 (16)	0.21654 (11)	0.0259 (3)
C14	0.2719 (2)	0.89901 (17)	0.20550 (11)	0.0269 (4)
H14	0.3301	0.8355	0.2235	0.032*
C15	0.0966 (2)	0.85853 (18)	0.16909 (11)	0.0293 (4)
H15	0.0364	0.7675	0.162	0.035*
C16	0.5484 (2)	1.08135 (16)	0.25871 (11)	0.0252 (3)
H16	0.6008	1.1726	0.2599	0.03*
C17	0.6520 (2)	1.01168 (16)	0.29644 (11)	0.0245 (3)
H17	0.6014	0.9209	0.2978	0.029*
C18	0.83523 (19)	1.06637 (15)	0.33494 (11)	0.0226 (3)
C19	0.9158 (2)	1.20092 (16)	0.34417 (12)	0.0267 (3)
H19	0.8495	1.259	0.3249	0.032*
C20	1.0898 (2)	1.25077 (15)	0.38084 (11)	0.0260 (3)
H20	1.1401	1.3434	0.3872	0.031*
C21	1.3748 (2)	1.23849 (17)	0.44935 (12)	0.0298 (4)
H21A	1.3997	1.3342	0.4498	0.045*
H21B	1.4499	1.2011	0.4123	0.045*
H21C	1.3973	1.2223	0.5136	0.045*
C22	0.94211 (19)	0.98455 (15)	0.36645 (10)	0.0216 (3)
C23	1.1223 (2)	1.04052 (15)	0.40176 (10)	0.0219 (3)
C24	1.2294 (2)	0.96115 (16)	0.43134 (11)	0.0264 (3)
H24	1.3508	0.9991	0.4523	0.032*
C25	1.1585 (2)	0.82932 (17)	0.42985 (12)	0.0290 (4)
H25	1.2308	0.7756	0.4499	0.035*
C26	0.9798 (2)	0.77316 (16)	0.39892 (12)	0.0280 (4)
H26	0.9308	0.6823	0.4006	0.034*
C27	0.8751 (2)	0.84764 (15)	0.36628 (11)	0.0243 (3)
H27	0.7551	0.8067	0.343	0.029*
N1	−0.17163 (19)	0.91167 (18)	0.11094 (11)	0.0405 (4)
N2	1.19082 (16)	1.17505 (13)	0.40782 (9)	0.0235 (3)
O1	0.34481 (16)	0.55102 (12)	0.39676 (8)	0.0347 (3)
O2	0.48631 (16)	0.45316 (13)	0.28231 (9)	0.0391 (3)
O3	0.46894 (16)	0.67913 (13)	0.28613 (11)	0.0452 (4)
S1	0.38860 (5)	0.54905 (4)	0.30368 (3)	0.02578 (14)
O4	0.76791 (17)	0.45303 (13)	0.42219 (11)	0.0367 (3)
H10	0.673 (3)	0.457 (2)	0.3841 (18)	0.058 (7)*
H2O	0.740 (3)	0.450 (2)	0.4763 (17)	0.043 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0200 (7)	0.0216 (7)	0.0291 (8)	0.0037 (6)	0.0026 (6)	0.0065 (6)
C2	0.0259 (8)	0.0303 (9)	0.0300 (9)	0.0077 (6)	0.0049 (7)	0.0026 (7)
C3	0.0210 (8)	0.0374 (9)	0.0403 (10)	0.0086 (7)	0.0064 (7)	0.0111 (8)
C4	0.0263 (9)	0.0379 (10)	0.0363 (10)	0.0064 (7)	−0.0029 (7)	0.0085 (8)
C5	0.0372 (10)	0.0642 (13)	0.0260 (9)	0.0189 (9)	−0.0026 (8)	−0.0026 (9)
C6	0.0268 (9)	0.0564 (12)	0.0287 (9)	0.0164 (8)	0.0062 (7)	0.0061 (8)
C7	0.0310 (10)	0.0609 (14)	0.0530 (13)	0.0075 (9)	−0.0131 (9)	0.0063 (10)
C8	0.0304 (10)	0.0841 (16)	0.0351 (10)	0.0246 (10)	0.0014 (8)	0.0144 (10)
C9	0.0243 (9)	0.0614 (13)	0.0407 (11)	0.0043 (8)	0.0002 (8)	−0.0086 (9)
C10	0.0230 (8)	0.0478 (11)	0.0214 (8)	0.0107 (7)	0.0038 (6)	0.0016 (7)
C11	0.0295 (9)	0.0433 (10)	0.0291 (9)	0.0176 (8)	0.0046 (7)	0.0073 (7)
C12	0.0283 (9)	0.0329 (9)	0.0288 (9)	0.0098 (7)	0.0061 (7)	0.0044 (7)
C13	0.0215 (8)	0.0324 (9)	0.0236 (8)	0.0074 (6)	0.0051 (6)	0.0029 (7)
C14	0.0232 (8)	0.0324 (9)	0.0246 (8)	0.0085 (6)	0.0032 (6)	0.0019 (7)
C15	0.0233 (8)	0.0369 (9)	0.0246 (8)	0.0051 (7)	0.0036 (6)	0.0003 (7)
C16	0.0230 (8)	0.0263 (8)	0.0250 (8)	0.0049 (6)	0.0056 (6)	0.0022 (6)
C17	0.0208 (8)	0.0247 (8)	0.0259 (8)	0.0037 (6)	0.0040 (6)	0.0018 (6)
C18	0.0206 (7)	0.0238 (8)	0.0218 (7)	0.0038 (6)	0.0050 (6)	0.0017 (6)
C19	0.0256 (8)	0.0235 (8)	0.0305 (9)	0.0062 (6)	0.0033 (7)	0.0054 (7)
C20	0.0271 (8)	0.0204 (8)	0.0289 (8)	0.0029 (6)	0.0056 (6)	0.0047 (6)
C21	0.0194 (8)	0.0303 (9)	0.0335 (9)	−0.0007 (6)	−0.0001 (7)	0.0018 (7)
C22	0.0221 (7)	0.0211 (7)	0.0202 (7)	0.0035 (6)	0.0056 (6)	0.0008 (6)
C23	0.0218 (7)	0.0225 (8)	0.0201 (7)	0.0037 (6)	0.0051 (6)	0.0015 (6)
C24	0.0229 (8)	0.0291 (8)	0.0266 (8)	0.0076 (6)	0.0033 (6)	0.0027 (6)
C25	0.0312 (9)	0.0287 (8)	0.0303 (9)	0.0134 (7)	0.0061 (7)	0.0050 (7)
C26	0.0315 (9)	0.0226 (8)	0.0307 (9)	0.0072 (6)	0.0103 (7)	0.0024 (7)
C27	0.0237 (8)	0.0221 (8)	0.0249 (8)	0.0030 (6)	0.0066 (6)	0.0005 (6)
N1	0.0213 (7)	0.0603 (11)	0.0371 (9)	0.0114 (7)	−0.0014 (6)	0.0044 (8)
N2	0.0196 (6)	0.0229 (7)	0.0240 (7)	0.0006 (5)	0.0022 (5)	0.0012 (5)
O1	0.0312 (7)	0.0368 (7)	0.0277 (6)	0.0002 (5)	−0.0011 (5)	−0.0009 (5)
O2	0.0274 (6)	0.0419 (7)	0.0451 (8)	0.0168 (5)	−0.0062 (5)	−0.0039 (6)
O3	0.0298 (7)	0.0310 (7)	0.0664 (9)	−0.0075 (5)	−0.0052 (6)	0.0215 (6)
S1	0.0194 (2)	0.0226 (2)	0.0321 (2)	0.00188 (14)	−0.00032 (15)	0.00509 (16)
O4	0.0290 (7)	0.0443 (8)	0.0389 (8)	0.0131 (6)	0.0054 (6)	0.0084 (6)

Geometric parameters (Å, º) top

C1—C6	1.379 (3)	C14—H14	0.95
C1—C2	1.385 (2)	C15—H15	0.95
C1—S1	1.771 (2)	C16—C17	1.348 (2)
C2—C3	1.384 (3)	C16—H16	0.95
C2—H2	0.95	C17—C18	1.447 (2)
C3—C4	1.380 (3)	C17—H17	0.95
C3—H3	0.95	C18—C19	1.390 (2)
C4—C5	1.384 (3)	C18—C22	1.433 (2)
C4—C7	1.506 (3)	C19—C20	1.372 (2)
C5—C6	1.384 (3)	C19—H19	0.95
C5—H5	0.95	C20—N2	1.328 (2)
C6—H6	0.95	C20—H20	0.95
C7—H7A	0.98	C21—N2	1.473 (2)
C7—H7B	0.98	C21—H21A	0.98
C7—H7C	0.98	C21—H21B	0.98
C8—N1	1.453 (3)	C21—H21C	0.98
C8—H8A	0.98	C22—C27	1.414 (2)
C8—H8B	0.98	C22—C23	1.418 (2)
C8—H8C	0.98	C23—N2	1.379 (2)
C9—N1	1.444 (3)	C23—C24	1.405 (2)
C9—H9A	0.98	C24—C25	1.366 (2)
C9—H9B	0.98	C24—H24	0.95
C9—H9C	0.98	C25—C26	1.398 (3)
C10—N1	1.368 (2)	C25—H25	0.95
C10—C11	1.400 (3)	C26—C27	1.365 (2)
C10—C15	1.413 (3)	C26—H26	0.95
C11—C12	1.379 (3)	C27—H27	0.95
C11—H11	0.95	O1—S1	1.4540 (15)
C12—C13	1.399 (2)	O2—S1	1.4502 (15)
C12—H12	0.95	O3—S1	1.4419 (16)
C13—C14	1.404 (3)	O4—H10	0.90 (3)
C13—C16	1.447 (2)	O4—H2O	0.86 (2)
C14—C15	1.375 (2)

C6—C1—C2	119.68 (16)	C10—C15—H15	119.4
C6—C1—S1	120.42 (13)	C17—C16—C13	127.15 (15)
C2—C1—S1	119.90 (13)	C17—C16—H16	116.4
C3—C2—C1	120.28 (17)	C13—C16—H16	116.4
C3—C2—H2	119.9	C16—C17—C18	124.17 (15)
C1—C2—H2	119.9	C16—C17—H17	117.9
C4—C3—C2	120.72 (17)	C18—C17—H17	117.9
C4—C3—H3	119.6	C19—C18—C22	116.75 (15)
C2—C3—H3	119.6	C19—C18—C17	121.72 (15)
C3—C4—C5	118.28 (16)	C22—C18—C17	121.53 (14)
C3—C4—C7	120.44 (18)	C20—C19—C18	120.79 (16)
C5—C4—C7	121.28 (19)	C20—C19—H19	119.6
C4—C5—C6	121.72 (18)	C18—C19—H19	119.6
C4—C5—H5	119.1	N2—C20—C19	122.84 (15)
C6—C5—H5	119.1	N2—C20—H20	118.6
C1—C6—C5	119.32 (17)	C19—C20—H20	118.6
C1—C6—H6	120.3	N2—C21—H21A	109.5
C5—C6—H6	120.3	N2—C21—H21B	109.5
C4—C7—H7A	109.5	H21A—C21—H21B	109.5
C4—C7—H7B	109.5	N2—C21—H21C	109.5
H7A—C7—H7B	109.5	H21A—C21—H21C	109.5
C4—C7—H7C	109.5	H21B—C21—H21C	109.5
H7A—C7—H7C	109.5	C27—C22—C23	117.05 (15)
H7B—C7—H7C	109.5	C27—C22—C18	122.72 (14)
N1—C8—H8A	109.5	C23—C22—C18	120.21 (14)
N1—C8—H8B	109.5	N2—C23—C24	120.25 (14)
H8A—C8—H8B	109.5	N2—C23—C22	118.87 (15)
N1—C8—H8C	109.5	C24—C23—C22	120.87 (15)
H8A—C8—H8C	109.5	C25—C24—C23	119.84 (15)
H8B—C8—H8C	109.5	C25—C24—H24	120.1
N1—C9—H9A	109.5	C23—C24—H24	120.1
N1—C9—H9B	109.5	C24—C25—C26	120.22 (16)
H9A—C9—H9B	109.5	C24—C25—H25	119.9
N1—C9—H9C	109.5	C26—C25—H25	119.9
H9A—C9—H9C	109.5	C27—C26—C25	120.68 (15)
H9B—C9—H9C	109.5	C27—C26—H26	119.7
N1—C10—C11	120.83 (17)	C25—C26—H26	119.7
N1—C10—C15	121.65 (17)	C26—C27—C22	121.24 (15)
C11—C10—C15	117.51 (16)	C26—C27—H27	119.4
C12—C11—C10	120.62 (17)	C22—C27—H27	119.4
C12—C11—H11	119.7	C10—N1—C9	121.38 (17)
C10—C11—H11	119.7	C10—N1—C8	120.21 (18)
C11—C12—C13	122.12 (17)	C9—N1—C8	117.97 (17)
C11—C12—H12	118.9	C20—N2—C23	120.50 (14)
C13—C12—H12	118.9	C20—N2—C21	118.80 (14)
C12—C13—C14	117.18 (15)	C23—N2—C21	120.61 (14)
C12—C13—C16	119.35 (16)	O3—S1—O2	113.25 (10)
C14—C13—C16	123.45 (16)	O3—S1—O1	113.06 (10)
C15—C14—C13	121.21 (16)	O2—S1—O1	111.98 (9)
C15—C14—H14	119.4	O3—S1—C1	106.47 (9)
C13—C14—H14	119.4	O2—S1—C1	105.80 (9)
C14—C15—C10	121.29 (17)	O1—S1—C1	105.52 (9)
C14—C15—H15	119.4	H10—O4—H2O	107 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H2O···O1ⁱ	0.86 (2)	2.07 (2)	2.922 (3)	175 (2)
O4—H10···O2	0.89 (2)	1.95 (3)	2.838 (3)	169 (2)
C14—H14···O3	0.95	2.41	3.359 (3)	174
C17—H17···O3	0.95	2.49	3.435 (3)	175
C27—H27···O3	0.95	2.34	3.282 (3)	172
C3—H3···O2ⁱⁱ	0.95	2.59	3.535 (3)	171
C20—H20···O1ⁱⁱⁱ	0.95	2.37	3.290 (3)	162

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

Acknowledgements

The authors thank the EPSRC for funding crystallographic facilities and for a postdoctoral grant to JAH (GR/M93864).

References

Alain, V., Blanchard-Desce, M., Ledoux-Rak, I. & Zyss, J. (2000). Chem. Commun. pp. 353–354. Web of Science CrossRef Google Scholar
Bahner, C. T., Pace, E. S. & Prevost, R. (1951). J. Am. Chem. Soc. 73, 3407–3408. CrossRef CAS Web of Science Google Scholar
Bhowmik, A. K., Tan, S., Ahyi, A. C., Mishra, A. & Thakur, M. (2000). Polym. Mater. Sci. Eng. 83, 169–170. CAS Google Scholar
Bosshard, Ch., Sutter, K., Prêtre, Ph., Hulliger, J., Flörsheimer, M., Kaatz, P. & Günter, P. (1995). Organic Nonlinear Optical Materials. Advances in Nonlinear Optics, Vol. 1. Amsterdam: Gordon & Breach. Google Scholar
Coe, B. J., Harris, J. A., Asselberghs, I., Clays, K., Olbrechts, G., Persoons, A., Hupp, J. T., Johnson, R. C., Coles, S. J., Hursthouse, M. B. & Nakatani, K. (2002). Adv. Funct. Mater. 12, 110–116. Web of Science CSD CrossRef CAS Google Scholar
Coe, B. J., Harris, J. A., Asselberghs, I., Wostyn, K., Clays, K., Persoons, A., Brunschwig, B. S., Coles, S. J., Gelbrich, T., Light, M. E., Hursthouse, M. B. & Nakatani, K. (2003). Adv. Funct. Mater. 13, 347–357. Web of Science CrossRef CAS Google Scholar
Duan, X.-M., Okada, S., Oikawa, H., Matsuda, H. & Nakanishi, H. (1995). Mol. Cryst. Liq. Cryst. 267, 89–94. CrossRef CAS Web of Science Google Scholar
Geis, W., Sinta, R., Mowers, W., Deneault, S. J., Marchant, M. F., Krohn, K. E., Spector, S. J., Calawa, D. R. & Lyszczarz, T. M. (2004). Appl. Phys. Lett. 84, 3729–3731. Web of Science CrossRef CAS Google Scholar
Hooft, R. (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Kaino, T., Cai, B. & Takayama, K. (2002). Adv. Funct. Mater. 12, 599–603. Web of Science CrossRef CAS Google Scholar
Lee, K.-S. & Kim, O.-K. (1999). Photonics Sci. News, 4, 9–20. CAS Google Scholar
Marder, S. R., Perry, J. W. & Schaefer, W. P. (1989). Science, 245, 626–628. CrossRef PubMed CAS Web of Science Google Scholar
Marder, S. R., Perry, J. W. & Yakymyshyn, C. P. (1994). Chem. Mater. 6, 1137–1147. CSD CrossRef CAS Web of Science Google Scholar
Meier, U., Bösch, M., Bosshard, Ch. & Günter, P. (2000). Synth. Met. 109, 19–22. Web of Science CrossRef CAS Google Scholar
Meier, U., Bösch, M., Bosshard, Ch., Pan, F. & Günter, P. (1998). J. Appl. Phys. 83, 3486–3489. Web of Science CrossRef CAS Google Scholar
Metzger, J., Larive, H., Dennilauler, R, Baralle, R. & Gaurat, C. (1969). Bull. Soc. Chim. Fr. pp. 1284–1293. Google Scholar
Mohan Kumar, R., Rajan Babu, D., Ravi, G. & Jayavel, R. (2003). J. Cryst. Growth, 250, 113–117. Web of Science CrossRef CAS Google Scholar
Nalwa, H. S. & Miyata, S. (1997). Editors. Nonlinear Optics of Organic Molecules and Polymers. Boca Raton: CRC Press. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press. Google Scholar
Oudar, J. L. & Chemla, D. S. (1977). J. Chem. Phys. 66, 2664–2668. CrossRef CAS Web of Science Google Scholar
Pan, F., Wong, M. S., Bosshard, Ch. & Günter, P. (1996). Adv. Mater. 8, 592–596. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sohma, S., Takahashi, H., Taniuchi, T. & Ito, H. (1999). Chem. Phys. 245, 359–364. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Taniuchi, T., Okada, S. & Nakanishi, H. (2004). J. Appl. Phys. 95, 5984–5988. Web of Science CrossRef CAS Google Scholar
Xu, X.-X., You, X.-Z. & Huang, X.-Y. (1995). Polyhedron, 14, 1815–1824. CSD CrossRef CAS Web of Science Google Scholar
Zyss, J. & Oudar, J. L. (1982). Phys. Rev. A, 26, 2016–2027. CrossRef Web of Science Google Scholar

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