4-{2-[4-(Dimethyl­amino)­phen­yl]ethen­yl}-1-methyl­pyridinium 2,4,6-trimethyl­benzene­sulfonate monohydrate

Li, Y.; Zhang, J.-X.; Fu, P.-Z.; Wu, Y.-C.

doi:10.1107/S1600536811007690

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o823

doi:10.1107/S1600536811007690

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4-{2-[4-(Dimethylamino)phenyl]ethenyl}-1-methylpyridinium 2,4,6-trimethylbenzenesulfonate monohydrate

Yin Li,^a ‡ Jian-Xiu Zhang,^a ^* Pei-Zhen Fu ^a and Yi-Cheng Wu ^a

^aKey Laboratory of Functional Crystal and Laser Technology, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China
^*Correspondence e-mail: zjx@mail.ipc.ac.cn

(Received 25 January 2011; accepted 1 March 2011; online 9 March 2011)

In the crystal structure of the title organic salt, C₁₆H₁₉N₂⁺·C₉H₁₁O₃S⁻·H₂O, the cations pack head-to-tail within a sheet and are aligned in opposite directions in neighboring sheets. The benzene ring of the anion makes an angle of 76.99 (6)° with the plane of the cationic chromophore. The cations are situated in the ab plane, whereas the benzene rings of the anions lie in the ac plane.

Related literature

For the crystal structure of solvent-free 2,4,6- trimethylbenzenesulfonate (DSTMS), see: Yang et al. (2007 ); Mutter et al. (2007 ). For the crystal structure of 4-N,N-dimethylamino-4′-N′-methylstilbazolium tosylate (DAST) and DAST·H₂O, see: Marder et al. (1989 ); Pan et al. (1996 ); Bryant et al. (1993 ). For the synthesis, see: Marder et al. (1994 ).

Experimental

Crystal data

C₁₆H₁₉N₂⁺·C₉H₁₁O₃S⁻·H₂O
M_r = 456.59
Triclinic, $[P \overline 1]$
a = 8.1993 (17) Å
b = 9.669 (2) Å
c = 15.247 (3) Å
α = 87.806 (7)°
β = 75.805 (6)°
γ = 83.239 (5)°
V = 1163.7 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 103 K
0.50 × 0.40 × 0.20 mm

Data collection

Rigaku AFC10/Saturn724+ diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.918, T_max = 0.966
11232 measured reflections
5240 independent reflections
4259 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.108
S = 1.00
5240 reflections
303 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS (Dowty, 1998 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811007690/im2263sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811007690/im2263Isup2.hkl

checkCIF report

Comment top

N,N-Dimethyl-{4-[2-(1'-methylpyridinium-4'-yl)-vinyl]-phenyl}-amine 2,4,6- trimethylbenzenesulfonate (DSTMS) is an organic nonlinear optical crystal, which is similar to 4-N,N-dimethylamino-4'-N'- methyl-stilbazolium tosylate (DAST). Both compounds show large nonlinear optical susceptibilities (Yang et al., 2007; Marder et al., 1989; Pan et al., 1996; Mutter et al., 2007). In the presence of water, orange DSTMS hydrate with no nonlinear optical effect is easy to obtain. Fig. 1 illustrates the molecular structure of DSTMS.H₂O together with the atomic numbering scheme. The C—H distances for the methyl groups are 0.98 Å, other H atoms are placed in idealized positions and constrained to have C—H=0.95 Å. The C—C distances for the phenyl groups range between 1.347 Å and 1.412 Å.

The unit cell of DSTMS.H₂O contains two (C₁₆H₁₉N₂)⁺ cations, two (C₉H₁₁O₃S)^- anions and two water molecules, with 1 symmetry. By comparing the data of geometric parameters of solvent free DSTMS and the hydrate, there are no obvious changes of bond distances and bond angles. In both compounds, the cations group pack head to tail within a sheet and are aligned in the opposite direction in the neighboring sheets. The phenyl rings in the anion group of DSTMS.H₂O lie at an angle of 76.99 (6)° relative to the cation chromophores, whereas the angle in the solvent free structure of DSTMS is 63.7 (2)°.

The crystal structure of DSTMS.H₂O (Fig. 2) is analogous to DAST.H₂O both belonging to triclinic space group P1 (Bryant et al., 1993). DSTMS.H₂O has two more methyl groups at the phenyl ring of the anion and the volume of unit cell therefore is larger compared with DAST.H₂O.

Related literature top

For the crystal structure of solvent-free 2,4,6- trimethylbenzenesulfonate (DSTMS), see: Yang et al. (2007); Mutter et al. (2007). For the crystal structure of 4-N,N-dimethylamino-4'-N'-methylstilbazolium tosylate (DAST) and DAST.H₂O, see: Marder et al. (1989); Pan et al. (1996); Bryant et al. (1993). For the synthesis, see: Marder et al. (1994).

Experimental top

DSTMS was synthesized by the condensation of 4-methyl-N-methyl pyridinium 2,4,6-trimethyl benzenesulfonate, which was prepared from 4-picoline and 2,4,6-trimethyl toluenesulfonate, and 4-N,N-dimethylamino-benzaldehyde in the presence of piperidine (Marder et al., 1994). A crystal of DSTMS.H₂O was grown by slow evaporation at room temperature from a saturated solution of DSTMS and 90% methanol/water.

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ATOMS (Dowty, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Thermal-ellipsoid (50% probability) plot showing the atomic numbering scheme.
	Fig. 2. Molecular packing plot of DSTMS.H₂O.

4-{2-[4-(Dimethylamino)phenyl]ethenyl}-1-methylpyridinium 2,4,6-trimethylbenzenesulfonate monohydrate top

Crystal data top

C₁₆H₁₉N₂⁺·C₉H₁₁O₃S⁻·H₂O	Z = 2
M_r = 456.59	F(000) = 488
Triclinic, P1	D_x = 1.303 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1993 (17) Å	Cell parameters from 3579 reflections
b = 9.669 (2) Å	θ = 3.2–27.5°
c = 15.247 (3) Å	µ = 0.17 mm⁻¹
α = 87.806 (7)°	T = 103 K
β = 75.805 (6)°	Chunk, red
γ = 83.239 (5)°	0.50 × 0.40 × 0.20 mm
V = 1163.7 (4) Å³

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	5240 independent reflections
Radiation source: Rotating Anode	4259 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ϕ and ω scans	h = −10→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −11→12
T_min = 0.918, T_max = 0.966	l = −19→19
11232 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0536P)² + 0.560P] where P = (F_o² + 2F_c²)/3
5240 reflections	(Δ/σ)_max = 0.001
303 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₆H₁₉N₂⁺·C₉H₁₁O₃S⁻·H₂O	γ = 83.239 (5)°
M_r = 456.59	V = 1163.7 (4) Å³
Triclinic, P1	Z = 2
a = 8.1993 (17) Å	Mo Kα radiation
b = 9.669 (2) Å	µ = 0.17 mm⁻¹
c = 15.247 (3) Å	T = 103 K
α = 87.806 (7)°	0.50 × 0.40 × 0.20 mm
β = 75.805 (6)°

Data collection top

Rigaku AFC10/Saturn724+ diffractometer	5240 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4259 reflections with I > 2σ(I)
T_min = 0.918, T_max = 0.966	R_int = 0.022
11232 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.70 e Å⁻³
5240 reflections	Δρ_min = −0.35 e Å⁻³
303 parameters

Special details top

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
S1	0.36608 (5)	0.78675 (4)	0.16984 (2)	0.01575 (11)
O1	0.51685 (14)	0.75321 (13)	0.20319 (8)	0.0232 (3)
O2	0.36736 (15)	0.92045 (12)	0.12167 (8)	0.0231 (3)
O3	0.33464 (15)	0.67560 (12)	0.11702 (8)	0.0235 (3)
N1	1.13709 (16)	0.36393 (14)	0.06835 (9)	0.0163 (3)
N2	−0.18615 (17)	0.31865 (14)	0.36790 (9)	0.0199 (3)
C1	1.0477 (2)	0.25780 (17)	0.06110 (11)	0.0194 (3)
H1	1.1037	0.1764	0.0292	0.023*
C2	0.8769 (2)	0.26638 (18)	0.09932 (11)	0.0215 (3)
H2	0.8158	0.1908	0.0940	0.026*
C3	0.7916 (2)	0.38704 (18)	0.14644 (11)	0.0204 (3)
C4	0.8883 (2)	0.49457 (18)	0.15010 (11)	0.0221 (3)
H4	0.8351	0.5788	0.1794	0.027*
C5	1.0588 (2)	0.48092 (17)	0.11214 (11)	0.0197 (3)
H5	1.1228	0.5549	0.1167	0.024*
C6	1.3204 (2)	0.35286 (19)	0.02549 (11)	0.0226 (4)
H6A	1.3378	0.3588	−0.0404	0.027*
H6B	1.3750	0.2634	0.0421	0.027*
H6C	1.3701	0.4290	0.0463	0.027*
C7	0.6116 (2)	0.40354 (18)	0.19219 (11)	0.0222 (3)
H7	0.5612	0.4933	0.2138	0.027*
C8	0.5143 (2)	0.29984 (17)	0.20536 (11)	0.0209 (3)
H8	0.5658	0.2119	0.1810	0.025*
C9	0.3364 (2)	0.30837 (18)	0.25350 (11)	0.0204 (3)
C10	0.2517 (2)	0.19128 (18)	0.25496 (11)	0.0213 (3)
H10	0.3134	0.1078	0.2282	0.026*
C11	0.0816 (2)	0.19291 (17)	0.29396 (10)	0.0189 (3)
H11	0.0281	0.1110	0.2939	0.023*
C12	−0.01440 (19)	0.31519 (16)	0.33420 (10)	0.0163 (3)
C13	0.0716 (2)	0.43197 (16)	0.33729 (11)	0.0202 (3)
H13	0.0117	0.5140	0.3670	0.024*
C14	0.2427 (2)	0.42795 (17)	0.29738 (11)	0.0213 (3)
H14	0.2983	0.5081	0.2997	0.026*
C15	−0.2692 (2)	0.19605 (18)	0.36304 (11)	0.0221 (3)
H15A	−0.2441	0.1659	0.3000	0.027*
H15B	−0.3918	0.2181	0.3858	0.027*
H15C	−0.2279	0.1212	0.4000	0.027*
C16	−0.2850 (2)	0.44394 (19)	0.40913 (13)	0.0295 (4)
H16A	−0.2528	0.4623	0.4650	0.035*
H16B	−0.4056	0.4316	0.4231	0.035*
H16C	−0.2634	0.5227	0.3671	0.035*
C17	0.02360 (19)	0.82889 (15)	0.24753 (10)	0.0154 (3)
C18	−0.1177 (2)	0.83123 (16)	0.32025 (11)	0.0174 (3)
H18	−0.2270	0.8412	0.3084	0.021*
C19	−0.1047 (2)	0.81959 (16)	0.40931 (11)	0.0183 (3)
C20	0.0562 (2)	0.80729 (17)	0.42491 (11)	0.0199 (3)
H20	0.0670	0.8027	0.4856	0.024*
C21	0.2030 (2)	0.80140 (16)	0.35469 (10)	0.0178 (3)
C22	0.18631 (19)	0.80801 (15)	0.26519 (10)	0.0143 (3)
C23	−0.0066 (2)	0.85704 (17)	0.15439 (11)	0.0211 (3)
H23A	−0.1263	0.8522	0.1567	0.025*
H23B	0.0635	0.7872	0.1122	0.025*
H23C	0.0233	0.9500	0.1338	0.025*
C24	−0.2586 (2)	0.8222 (2)	0.48747 (11)	0.0261 (4)
H24A	−0.3611	0.8382	0.4646	0.031*
H24B	−0.2578	0.8972	0.5287	0.031*
H24C	−0.2570	0.7327	0.5199	0.031*
C25	0.3698 (2)	0.7919 (2)	0.38181 (12)	0.0287 (4)
H25A	0.3481	0.8006	0.4476	0.034*
H25B	0.4343	0.8671	0.3521	0.034*
H25C	0.4350	0.7017	0.3632	0.034*
O4	0.69606 (17)	1.00845 (14)	0.04707 (10)	0.0259 (3)
H4A	0.611 (3)	0.977 (3)	0.0748 (18)	0.053 (8)*
H4B	0.675 (3)	1.039 (3)	−0.0023 (18)	0.050 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01557 (19)	0.01519 (19)	0.01466 (18)	−0.00387 (14)	0.00108 (14)	−0.00183 (13)
O1	0.0144 (5)	0.0307 (7)	0.0228 (6)	−0.0005 (5)	−0.0015 (5)	−0.0032 (5)
O2	0.0271 (6)	0.0198 (6)	0.0196 (6)	−0.0058 (5)	0.0006 (5)	0.0033 (4)
O3	0.0215 (6)	0.0238 (6)	0.0230 (6)	−0.0079 (5)	0.0028 (5)	−0.0095 (5)
N1	0.0142 (6)	0.0215 (7)	0.0136 (6)	−0.0040 (5)	−0.0028 (5)	0.0006 (5)
N2	0.0143 (6)	0.0190 (7)	0.0240 (7)	−0.0016 (5)	0.0001 (5)	−0.0006 (5)
C1	0.0218 (8)	0.0198 (8)	0.0186 (8)	−0.0046 (6)	−0.0077 (6)	0.0004 (6)
C2	0.0218 (8)	0.0247 (8)	0.0217 (8)	−0.0100 (7)	−0.0098 (7)	0.0048 (6)
C3	0.0183 (8)	0.0276 (9)	0.0160 (7)	−0.0042 (7)	−0.0058 (6)	0.0073 (6)
C4	0.0212 (8)	0.0242 (8)	0.0198 (8)	−0.0014 (7)	−0.0031 (6)	0.0000 (6)
C5	0.0205 (8)	0.0207 (8)	0.0179 (8)	−0.0056 (6)	−0.0033 (6)	−0.0005 (6)
C6	0.0136 (7)	0.0326 (9)	0.0202 (8)	−0.0046 (7)	−0.0002 (6)	−0.0015 (7)
C7	0.0229 (8)	0.0219 (8)	0.0219 (8)	−0.0007 (7)	−0.0064 (7)	0.0010 (6)
C8	0.0200 (8)	0.0229 (8)	0.0202 (8)	−0.0011 (6)	−0.0061 (6)	0.0006 (6)
C9	0.0163 (8)	0.0277 (9)	0.0164 (7)	0.0005 (6)	−0.0041 (6)	0.0034 (6)
C10	0.0198 (8)	0.0236 (8)	0.0190 (8)	0.0026 (6)	−0.0042 (6)	−0.0025 (6)
C11	0.0203 (8)	0.0175 (8)	0.0186 (8)	−0.0010 (6)	−0.0045 (6)	−0.0016 (6)
C12	0.0159 (7)	0.0176 (7)	0.0146 (7)	−0.0010 (6)	−0.0029 (6)	0.0021 (6)
C13	0.0190 (8)	0.0157 (7)	0.0248 (8)	0.0005 (6)	−0.0046 (6)	0.0002 (6)
C14	0.0213 (8)	0.0187 (8)	0.0255 (8)	−0.0057 (6)	−0.0078 (7)	0.0048 (6)
C15	0.0199 (8)	0.0244 (8)	0.0222 (8)	−0.0057 (7)	−0.0046 (6)	0.0039 (6)
C16	0.0182 (8)	0.0279 (9)	0.0363 (10)	0.0028 (7)	0.0034 (7)	−0.0055 (8)
C17	0.0176 (7)	0.0116 (7)	0.0167 (7)	−0.0005 (6)	−0.0043 (6)	0.0004 (5)
C18	0.0151 (7)	0.0165 (7)	0.0204 (8)	−0.0010 (6)	−0.0042 (6)	−0.0005 (6)
C19	0.0170 (8)	0.0173 (8)	0.0181 (7)	−0.0018 (6)	0.0001 (6)	0.0007 (6)
C20	0.0197 (8)	0.0262 (8)	0.0132 (7)	−0.0023 (7)	−0.0027 (6)	0.0006 (6)
C21	0.0159 (7)	0.0196 (8)	0.0179 (7)	−0.0021 (6)	−0.0040 (6)	−0.0004 (6)
C22	0.0146 (7)	0.0115 (7)	0.0151 (7)	−0.0020 (5)	0.0005 (6)	−0.0014 (5)
C23	0.0228 (8)	0.0232 (8)	0.0180 (8)	−0.0004 (7)	−0.0074 (6)	0.0015 (6)
C24	0.0193 (8)	0.0344 (10)	0.0201 (8)	−0.0005 (7)	0.0025 (7)	0.0008 (7)
C25	0.0191 (8)	0.0506 (12)	0.0169 (8)	−0.0021 (8)	−0.0058 (7)	−0.0031 (8)
O4	0.0243 (7)	0.0278 (7)	0.0286 (7)	−0.0110 (5)	−0.0098 (6)	0.0085 (5)

Geometric parameters (Å, º) top

S1—O1	1.4468 (12)	C12—C13	1.408 (2)
S1—O3	1.4503 (11)	C13—C14	1.382 (2)
S1—O2	1.4619 (12)	C13—H13	0.9500
S1—C22	1.7969 (15)	C14—H14	0.9500
N1—C5	1.347 (2)	C15—H15A	0.9800
N1—C1	1.352 (2)	C15—H15B	0.9800
N1—C6	1.478 (2)	C15—H15C	0.9800
N2—C12	1.372 (2)	C16—H16A	0.9800
N2—C15	1.448 (2)	C16—H16B	0.9800
N2—C16	1.448 (2)	C16—H16C	0.9800
C1—C2	1.372 (2)	C17—C18	1.392 (2)
C1—H1	0.9500	C17—C22	1.415 (2)
C2—C3	1.411 (2)	C17—C23	1.510 (2)
C2—H2	0.9500	C18—C19	1.387 (2)
C3—C4	1.390 (2)	C18—H18	0.9500
C3—C7	1.463 (2)	C19—C20	1.388 (2)
C4—C5	1.369 (2)	C19—C24	1.507 (2)
C4—H4	0.9500	C20—C21	1.398 (2)
C5—H5	0.9500	C20—H20	0.9500
C6—H6A	0.9800	C21—C22	1.403 (2)
C6—H6B	0.9800	C21—C25	1.515 (2)
C6—H6C	0.9800	C23—H23A	0.9800
C7—C8	1.333 (2)	C23—H23B	0.9800
C7—H7	0.9500	C23—H23C	0.9800
C8—C9	1.457 (2)	C24—H24A	0.9800
C8—H8	0.9500	C24—H24B	0.9800
C9—C10	1.393 (2)	C24—H24C	0.9800
C9—C14	1.405 (2)	C25—H25A	0.9800
C10—C11	1.374 (2)	C25—H25B	0.9800
C10—H10	0.9500	C25—H25C	0.9800
C11—C12	1.412 (2)	O4—H4A	0.81 (3)
C11—H11	0.9500	O4—H4B	0.85 (3)

O1—S1—O3	112.80 (7)	C12—C13—H13	119.8
O1—S1—O2	111.61 (7)	C13—C14—C9	121.66 (15)
O3—S1—O2	112.36 (7)	C13—C14—H14	119.2
O1—S1—C22	108.39 (7)	C9—C14—H14	119.2
O3—S1—C22	105.54 (7)	N2—C15—H15A	109.5
O2—S1—C22	105.59 (7)	N2—C15—H15B	109.5
C5—N1—C1	120.26 (14)	H15A—C15—H15B	109.5
C5—N1—C6	120.03 (13)	N2—C15—H15C	109.5
C1—N1—C6	119.69 (13)	H15A—C15—H15C	109.5
C12—N2—C15	119.93 (13)	H15B—C15—H15C	109.5
C12—N2—C16	120.42 (14)	N2—C16—H16A	109.5
C15—N2—C16	119.65 (14)	N2—C16—H16B	109.5
N1—C1—C2	120.76 (15)	H16A—C16—H16B	109.5
N1—C1—H1	119.6	N2—C16—H16C	109.5
C2—C1—H1	119.6	H16A—C16—H16C	109.5
C1—C2—C3	120.28 (15)	H16B—C16—H16C	109.5
C1—C2—H2	119.9	C18—C17—C22	118.60 (14)
C3—C2—H2	119.9	C18—C17—C23	117.57 (14)
C4—C3—C2	116.78 (15)	C22—C17—C23	123.74 (14)
C4—C3—C7	119.04 (15)	C19—C18—C17	122.41 (15)
C2—C3—C7	124.16 (15)	C19—C18—H18	118.8
C5—C4—C3	121.03 (16)	C17—C18—H18	118.8
C5—C4—H4	119.5	C18—C19—C20	117.74 (14)
C3—C4—H4	119.5	C18—C19—C24	121.92 (15)
N1—C5—C4	120.85 (15)	C20—C19—C24	120.33 (15)
N1—C5—H5	119.6	C19—C20—C21	122.50 (15)
C4—C5—H5	119.6	C19—C20—H20	118.7
N1—C6—H6A	109.5	C21—C20—H20	118.7
N1—C6—H6B	109.5	C20—C21—C22	118.52 (14)
H6A—C6—H6B	109.5	C20—C21—C25	116.73 (14)
N1—C6—H6C	109.5	C22—C21—C25	124.74 (14)
H6A—C6—H6C	109.5	C21—C22—C17	120.04 (14)
H6B—C6—H6C	109.5	C21—C22—S1	122.28 (12)
C8—C7—C3	123.74 (16)	C17—C22—S1	117.66 (11)
C8—C7—H7	118.1	C17—C23—H23A	109.5
C3—C7—H7	118.1	C17—C23—H23B	109.5
C7—C8—C9	126.30 (16)	H23A—C23—H23B	109.5
C7—C8—H8	116.9	C17—C23—H23C	109.5
C9—C8—H8	116.8	H23A—C23—H23C	109.5
C10—C9—C14	117.34 (15)	H23B—C23—H23C	109.5
C10—C9—C8	118.18 (15)	C19—C24—H24A	109.5
C14—C9—C8	124.46 (16)	C19—C24—H24B	109.5
C11—C10—C9	121.99 (15)	H24A—C24—H24B	109.5
C11—C10—H10	119.0	C19—C24—H24C	109.5
C9—C10—H10	119.0	H24A—C24—H24C	109.5
C10—C11—C12	120.65 (15)	H24B—C24—H24C	109.5
C10—C11—H11	119.7	C21—C25—H25A	109.5
C12—C11—H11	119.7	C21—C25—H25B	109.5
N2—C12—C13	121.89 (14)	H25A—C25—H25B	109.5
N2—C12—C11	120.30 (14)	C21—C25—H25C	109.5
C13—C12—C11	117.81 (14)	H25A—C25—H25C	109.5
C14—C13—C12	120.40 (15)	H25B—C25—H25C	109.5
C14—C13—H13	119.8	H4A—O4—H4B	105 (2)

C5—N1—C1—C2	−1.1 (2)	C12—C13—C14—C9	−0.6 (2)
C6—N1—C1—C2	−179.16 (14)	C10—C9—C14—C13	−2.6 (2)
N1—C1—C2—C3	0.4 (2)	C8—C9—C14—C13	176.07 (15)
C1—C2—C3—C4	1.1 (2)	C22—C17—C18—C19	2.7 (2)
C1—C2—C3—C7	−177.60 (15)	C23—C17—C18—C19	−173.92 (14)
C2—C3—C4—C5	−2.1 (2)	C17—C18—C19—C20	1.0 (2)
C7—C3—C4—C5	176.71 (15)	C17—C18—C19—C24	−179.96 (15)
C1—N1—C5—C4	0.1 (2)	C18—C19—C20—C21	−2.3 (2)
C6—N1—C5—C4	178.19 (15)	C24—C19—C20—C21	178.59 (15)
C3—C4—C5—N1	1.5 (3)	C19—C20—C21—C22	−0.1 (2)
C4—C3—C7—C8	−168.78 (16)	C19—C20—C21—C25	178.41 (16)
C2—C3—C7—C8	9.9 (3)	C20—C21—C22—C17	3.9 (2)
C3—C7—C8—C9	177.35 (15)	C25—C21—C22—C17	−174.51 (15)
C7—C8—C9—C10	175.50 (16)	C20—C21—C22—S1	−174.67 (12)
C7—C8—C9—C14	−3.2 (3)	C25—C21—C22—S1	7.0 (2)
C14—C9—C10—C11	2.8 (2)	C18—C17—C22—C21	−5.1 (2)
C8—C9—C10—C11	−175.95 (15)	C23—C17—C22—C21	171.28 (14)
C9—C10—C11—C12	0.2 (2)	C18—C17—C22—S1	173.46 (11)
C15—N2—C12—C13	179.87 (15)	C23—C17—C22—S1	−10.1 (2)
C16—N2—C12—C13	−0.7 (2)	O1—S1—C22—C21	4.19 (15)
C15—N2—C12—C11	0.6 (2)	O3—S1—C22—C21	125.28 (13)
C16—N2—C12—C11	−179.95 (15)	O2—S1—C22—C21	−115.53 (13)
C10—C11—C12—N2	175.85 (14)	O1—S1—C22—C17	−174.38 (11)
C10—C11—C12—C13	−3.4 (2)	O3—S1—C22—C17	−53.28 (13)
N2—C12—C13—C14	−175.66 (15)	O2—S1—C22—C17	65.90 (13)
C11—C12—C13—C14	3.6 (2)

Experimental details

Crystal data
Chemical formula	C₁₆H₁₉N₂⁺·C₉H₁₁O₃S⁻·H₂O
M_r	456.59
Crystal system, space group	Triclinic, P1
Temperature (K)	103
a, b, c (Å)	8.1993 (17), 9.669 (2), 15.247 (3)
α, β, γ (°)	87.806 (7), 75.805 (6), 83.239 (5)
V (Å³)	1163.7 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.50 × 0.40 × 0.20

Data collection
Diffractometer	Rigaku AFC10/Saturn724+ diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.918, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	11232, 5240, 4259
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.108, 1.00
No. of reflections	5240
No. of parameters	303
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.35

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ATOMS (Dowty, 1998).

Footnotes

‡Current address; Graduate University of the Chinese Academy of Sciences, Beijing 100039, People's Republic of China.

Acknowledgements

The authors thank Professor Kaibei Yu, State Key Laboratory of Explosion Science and Technology of Beijing Institute of Technology, for the data collection. This work was supported by the National Basic Research Project of China (No. 2010CB630701).

References

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