4-(3-Eth-oxy-4-hydroxy-styr-yl)-1-methyl-pyridinium tosyl-ate monohydrate.

In the title compound, C(16)H(18)NO(2) (+)·C(7)H(7)O(3)S(-)·H(2)O, the dihedral angle between the pyridyl and benzene rings of the pyridinium cation is 0.2 (1)°. The benzene ring of the tosyl-ate anion makes a dihedral angle of 4.8 (2)° with the best mean plane of the pyridinium cation. The pyridinium cation and the tosyl-ate anion are hydrogen bonded to the water mol-ecule, and the crystal packing is further stabilized by inter-molecular C-H⋯O and π-π inter-actions [centroid-centroid separations of 3.648 (3) and 3.594 (2) Å.

Related literature

For a related structure, see: Zhang et al. (1997 ▶). For mol­ecular compounds with non-linear optical properties, see: Bosshard et al. (1995 ▶); Nalwa & Miyata (1997 ▶); Lee & Kim (1999 ▶).

Experimental

Crystal data

C16H18NO2 +·C7H7O3S−·H2O

M = 445.52

Monoclinic,

a = 13.7700 (4) Å

b = 9.7125 (2) Å

c = 17.3394 (5) Å

β = 104.059 (2)°

V = 2249.53 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.18 mm−1

T = 293 (2) K

0.25 × 0.17 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.961, T max = 0.975

48719 measured reflections

5310 independent reflections

3610 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.187

S = 1.03

5310 reflections

290 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.72 e Å−3

Δρmin = −0.30 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041007/lx2079sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041007/lx2079Isup2.hkl

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

C16H18NO2+·C7H7O3S−·H2O	F(000) = 944
Mr = 445.52	Dx = 1.315 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5318 reflections
a = 13.7700 (4) Å	θ = 2.2–27.8°
b = 9.7125 (2) Å	µ = 0.18 mm−1
c = 17.3394 (5) Å	T = 293 K
β = 104.059 (2)°	Block, orange
V = 2249.53 (10) Å3	0.25 × 0.17 × 0.16 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	5310 independent reflections
Radiation source: fine-focus sealed tube	3610 reflections with I > 2σ(I)
graphite	Rint = 0.034
Detector resolution: 10 pixels mm-1	θmax = 27.8°, θmin = 2.2°
ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→12
Tmin = 0.961, Tmax = 0.975	l = −22→22
48719 measured reflections

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)] = 0.057	Hydrogen site location: difference Fourier map
wR(F2) = 0.187	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0893P)2 + 1.1253P] where P = (Fo2 + 2Fc2)/3
5310 reflections	(Δ/σ)max < 0.001
290 parameters	Δρmax = 0.72 e Å−3
3 restraints	Δρmin = −0.30 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

	x	y	z	Uiso*/Ueq
S	0.72581 (5)	0.48936 (6)	0.59449 (4)	0.0646 (2)
O1	0.92457 (12)	0.27591 (17)	0.20090 (10)	0.0589 (4)
H1O	0.9248	0.2213	0.1649	0.088*
O2	0.91242 (13)	0.42417 (17)	0.32358 (10)	0.0604 (4)
O3	0.62950 (16)	0.5133 (2)	0.61455 (17)	0.0998 (8)
O4	0.78329 (17)	0.3912 (2)	0.64784 (16)	0.0958 (8)
O5	0.7116 (2)	0.4619 (2)	0.51204 (15)	0.1024 (8)
O6	0.44858 (19)	0.3921 (3)	0.58789 (15)	0.0855 (6)
H6OA	0.399 (2)	0.427 (3)	0.5530 (19)	0.16 (2)*
H6OB	0.4608 (18)	0.4682 (16)	0.6128 (13)	0.050 (7)*
N	0.55785 (13)	−0.0896 (2)	0.63677 (11)	0.0514 (5)
C1	0.56915 (16)	−0.1585 (2)	0.57240 (14)	0.0515 (5)
H1	0.5445	−0.2477	0.5633	0.062*
C2	0.61625 (16)	−0.0993 (2)	0.52038 (13)	0.0484 (5)
H2	0.6230	−0.1481	0.4758	0.058*
C3	0.65447 (15)	0.0336 (2)	0.53320 (13)	0.0477 (5)
C4	0.64007 (18)	0.1008 (2)	0.60023 (15)	0.0565 (6)
H4	0.6637	0.1902	0.6110	0.068*
C5	0.59222 (18)	0.0384 (3)	0.65010 (15)	0.0571 (6)
H5	0.5832	0.0856	0.6945	0.069*
C6	0.5107 (2)	−0.1567 (4)	0.69445 (17)	0.0814 (9)
H6A	0.5615	−0.1870	0.7395	0.122*
H6B	0.4723	−0.2345	0.6699	0.122*
H6C	0.4673	−0.0924	0.7116	0.122*
C7	0.70733 (17)	0.1044 (2)	0.48149 (14)	0.0547 (6)
H7	0.7258	0.1957	0.4928	0.066*
C8	0.73041 (18)	0.0465 (3)	0.41971 (15)	0.0578 (6)
H8	0.7107	−0.0447	0.4098	0.069*
C9	0.78346 (17)	0.1085 (3)	0.36470 (14)	0.0545 (6)
C10	0.79432 (19)	0.0317 (3)	0.30061 (16)	0.0616 (6)
H10	0.7700	−0.0580	0.2944	0.074*
C11	0.84097 (18)	0.0864 (3)	0.24558 (15)	0.0581 (6)
H11	0.8466	0.0335	0.2022	0.070*
C12	0.87921 (16)	0.2176 (2)	0.25382 (13)	0.0486 (5)
C13	0.87119 (17)	0.2968 (2)	0.31965 (13)	0.0503 (5)
C14	0.82272 (17)	0.2423 (3)	0.37394 (13)	0.0541 (5)
H14	0.8161	0.2952	0.4171	0.065*
C15	0.9068 (2)	0.5061 (3)	0.39048 (17)	0.0719 (8)
H15A	0.9420	0.4613	0.4393	0.086*
H15B	0.8376	0.5191	0.3922	0.086*
C16	0.9543 (3)	0.6418 (4)	0.3816 (2)	0.1043 (13)
H16A	0.9518	0.6998	0.4259	0.156*
H16B	0.9189	0.6851	0.3332	0.156*
H16C	1.0228	0.6276	0.3801	0.156*
C17	0.78797 (16)	0.6487 (2)	0.61343 (14)	0.0476 (5)
C18	0.8387 (2)	0.7012 (3)	0.56113 (17)	0.0652 (7)
H18	0.8428	0.6513	0.5163	0.078*
C19	0.8839 (2)	0.8288 (3)	0.5755 (2)	0.0784 (9)
H19	0.9184	0.8637	0.5398	0.094*
C20	0.8792 (2)	0.9043 (3)	0.6399 (2)	0.0763 (9)
C21	0.8292 (2)	0.8499 (3)	0.69306 (18)	0.0749 (9)
H21	0.8265	0.8996	0.7383	0.090*
C22	0.78351 (19)	0.7234 (3)	0.67996 (14)	0.0592 (6)
H22	0.7496	0.6884	0.7160	0.071*
C23	0.9251 (3)	1.0473 (3)	0.6528 (3)	0.133 (2)
H23A	0.9759	1.0560	0.6237	0.200*
H23B	0.9543	1.0611	0.7084	0.200*
H23C	0.8740	1.1151	0.6343	0.200*

	U11	U22	U33	U12	U13	U23
S	0.0666 (4)	0.0422 (3)	0.0802 (5)	−0.0071 (3)	0.0084 (3)	0.0070 (3)
O1	0.0698 (10)	0.0593 (9)	0.0532 (9)	−0.0040 (8)	0.0257 (8)	−0.0002 (7)
O2	0.0762 (11)	0.0561 (9)	0.0528 (9)	−0.0154 (8)	0.0230 (8)	−0.0076 (7)
O3	0.0602 (12)	0.0806 (14)	0.156 (2)	−0.0146 (10)	0.0220 (13)	0.0169 (14)
O4	0.0885 (14)	0.0532 (11)	0.133 (2)	0.0007 (10)	0.0020 (13)	0.0301 (12)
O5	0.140 (2)	0.0646 (12)	0.0956 (17)	−0.0186 (13)	0.0156 (15)	−0.0220 (12)
O6	0.0890 (16)	0.0924 (16)	0.0747 (14)	−0.0218 (13)	0.0189 (12)	0.0171 (13)
N	0.0447 (10)	0.0609 (11)	0.0485 (11)	0.0068 (8)	0.0112 (8)	0.0105 (9)
C1	0.0492 (12)	0.0417 (10)	0.0614 (14)	0.0022 (9)	0.0090 (10)	0.0038 (10)
C2	0.0493 (11)	0.0485 (11)	0.0476 (12)	0.0041 (9)	0.0124 (9)	−0.0017 (9)
C3	0.0425 (11)	0.0489 (11)	0.0498 (12)	0.0038 (9)	0.0074 (9)	0.0055 (9)
C4	0.0575 (13)	0.0452 (11)	0.0642 (15)	0.0007 (10)	0.0101 (11)	−0.0056 (10)
C5	0.0561 (13)	0.0622 (14)	0.0523 (13)	0.0067 (11)	0.0121 (11)	−0.0102 (11)
C6	0.0753 (18)	0.109 (2)	0.0651 (18)	0.0012 (17)	0.0274 (14)	0.0299 (16)
C7	0.0548 (13)	0.0484 (11)	0.0597 (14)	−0.0057 (10)	0.0116 (11)	0.0003 (10)
C8	0.0580 (14)	0.0521 (12)	0.0621 (15)	−0.0083 (10)	0.0120 (11)	−0.0001 (11)
C9	0.0495 (12)	0.0610 (13)	0.0528 (13)	−0.0070 (10)	0.0125 (10)	0.0046 (10)
C10	0.0634 (15)	0.0551 (13)	0.0673 (16)	−0.0108 (11)	0.0179 (12)	−0.0025 (11)
C11	0.0614 (14)	0.0585 (13)	0.0563 (14)	−0.0046 (11)	0.0181 (11)	−0.0078 (11)
C12	0.0448 (11)	0.0556 (12)	0.0451 (12)	0.0015 (9)	0.0105 (9)	0.0028 (9)
C13	0.0499 (12)	0.0525 (12)	0.0463 (12)	−0.0036 (9)	0.0072 (9)	−0.0002 (9)
C14	0.0550 (13)	0.0624 (13)	0.0453 (12)	−0.0024 (10)	0.0131 (10)	−0.0032 (10)
C15	0.094 (2)	0.0704 (16)	0.0586 (15)	−0.0280 (14)	0.0324 (14)	−0.0164 (12)
C16	0.163 (3)	0.077 (2)	0.098 (2)	−0.052 (2)	0.079 (2)	−0.0346 (18)
C17	0.0463 (11)	0.0381 (10)	0.0570 (13)	0.0030 (8)	0.0101 (9)	0.0011 (9)
C18	0.0755 (16)	0.0488 (12)	0.0830 (18)	−0.0006 (11)	0.0420 (14)	−0.0084 (12)
C19	0.0653 (16)	0.0535 (14)	0.127 (3)	−0.0044 (12)	0.0430 (17)	0.0067 (16)
C20	0.0515 (14)	0.0437 (12)	0.119 (3)	0.0022 (11)	−0.0074 (15)	−0.0091 (15)
C21	0.0733 (17)	0.0632 (15)	0.0715 (18)	0.0183 (14)	−0.0146 (14)	−0.0236 (14)
C22	0.0603 (14)	0.0656 (14)	0.0489 (13)	0.0136 (11)	0.0076 (11)	0.0035 (11)
C23	0.083 (2)	0.0527 (17)	0.234 (6)	−0.0123 (16)	−0.021 (3)	−0.023 (3)

S—O5	1.420 (3)	C9—C10	1.377 (4)
S—O4	1.427 (2)	C9—C14	1.401 (3)
S—O3	1.469 (2)	C10—C11	1.380 (3)
S—C17	1.760 (2)	C10—H10	0.9300
O1—C12	1.353 (3)	C11—C12	1.373 (3)
O1—H1O	0.8200	C11—H11	0.9300
O2—C13	1.356 (3)	C12—C13	1.403 (3)
O2—C15	1.424 (3)	C13—C14	1.385 (3)
O6—H6OA	0.86 (3)	C14—H14	0.9300
O6—H6OB	0.85 (1)	C15—C16	1.496 (4)
N—C5	1.330 (3)	C15—H15A	0.9700
N—C1	1.342 (3)	C15—H15B	0.9700
N—C6	1.471 (3)	C16—H16A	0.9600
C1—C2	1.360 (3)	C16—H16B	0.9600
C1—H1	0.9300	C16—H16C	0.9600
C2—C3	1.391 (3)	C17—C18	1.371 (3)
C2—H2	0.9300	C17—C22	1.377 (3)
C3—C4	1.389 (3)	C18—C19	1.382 (4)
C3—C7	1.457 (3)	C18—H18	0.9300
C4—C5	1.351 (4)	C19—C20	1.351 (5)
C4—H4	0.9300	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.383 (5)
C6—H6A	0.9600	C20—C23	1.519 (4)
C6—H6B	0.9600	C21—C22	1.373 (4)
C6—H6C	0.9600	C21—H21	0.9300
C7—C8	1.315 (3)	C22—H22	0.9300
C7—H7	0.9300	C23—H23A	0.9600
C8—C9	1.465 (3)	C23—H23B	0.9600
C8—H8	0.9300	C23—H23C	0.9600
O5—S—O4	116.5 (2)	C10—C11—H11	119.4
O5—S—O3	110.9 (2)	O1—C12—C11	123.1 (2)
O4—S—O3	110.04 (15)	O1—C12—C13	117.6 (2)
O5—S—C17	107.1 (1)	C11—C12—C13	119.3 (2)
O4—S—C17	107.4 (1)	O2—C13—C14	125.4 (2)
O3—S—C17	104.1 (1)	O2—C13—C12	115.2 (2)
C12—O1—H1O	109.5	C14—C13—C12	119.3 (2)
C13—O2—C15	116.5 (2)	C13—C14—C9	120.9 (2)
H6OA—O6—H6OB	92 (1)	C13—C14—H14	119.6
C5—N—C1	120.1 (2)	C9—C14—H14	119.6
C5—N—C6	119.6 (2)	O2—C15—C16	107.3 (2)
C1—N—C6	120.2 (2)	O2—C15—H15A	110.3
N—C1—C2	120.7 (2)	C16—C15—H15A	110.3
N—C1—H1	119.6	O2—C15—H15B	110.3
C2—C1—H1	119.6	C16—C15—H15B	110.3
C1—C2—C3	120.6 (2)	H15A—C15—H15B	108.5
C1—C2—H2	119.7	C15—C16—H16A	109.5
C3—C2—H2	119.7	C15—C16—H16B	109.5
C4—C3—C2	116.4 (2)	H16A—C16—H16B	109.5
C4—C3—C7	119.2 (2)	C15—C16—H16C	109.5
C2—C3—C7	124.5 (2)	H16A—C16—H16C	109.5
C5—C4—C3	121.0 (2)	H16B—C16—H16C	109.5
C5—C4—H4	119.5	C18—C17—C22	119.4 (2)
C3—C4—H4	119.5	C18—C17—S	120.46 (18)
N—C5—C4	121.1 (2)	C22—C17—S	120.07 (19)
N—C5—H5	119.5	C17—C18—C19	119.6 (3)
C4—C5—H5	119.5	C17—C18—H18	120.2
N—C6—H6A	109.5	C19—C18—H18	120.2
N—C6—H6B	109.5	C20—C19—C18	121.8 (3)
H6A—C6—H6B	109.5	C20—C19—H19	119.1
N—C6—H6C	109.5	C18—C19—H19	119.1
H6A—C6—H6C	109.5	C19—C20—C21	118.3 (2)
H6B—C6—H6C	109.5	C19—C20—C23	121.1 (4)
C8—C7—C3	123.7 (2)	C21—C20—C23	120.6 (3)
C8—C7—H7	118.2	C22—C21—C20	121.0 (3)
C3—C7—H7	118.2	C22—C21—H21	119.5
C7—C8—C9	127.7 (2)	C20—C21—H21	119.5
C7—C8—H8	116.1	C21—C22—C17	119.9 (3)
C9—C8—H8	116.1	C21—C22—H22	120.1
C10—C9—C14	118.7 (2)	C17—C22—H22	120.1
C10—C9—C8	118.1 (2)	C20—C23—H23A	109.5
C14—C9—C8	123.1 (2)	C20—C23—H23B	109.5
C9—C10—C11	120.6 (2)	H23A—C23—H23B	109.5
C9—C10—H10	119.7	C20—C23—H23C	109.5
C11—C10—H10	119.7	H23A—C23—H23C	109.5
C12—C11—C10	121.1 (2)	H23B—C23—H23C	109.5
C12—C11—H11	119.4
C5—N—C1—C2	0.5 (3)	O1—C12—C13—C14	178.16 (19)
C6—N—C1—C2	−177.3 (2)	C11—C12—C13—C14	−1.6 (3)
N—C1—C2—C3	0.5 (3)	O2—C13—C14—C9	−179.4 (2)
C1—C2—C3—C4	−1.1 (3)	C12—C13—C14—C9	1.2 (3)
C1—C2—C3—C7	179.0 (2)	C10—C9—C14—C13	0.3 (4)
C2—C3—C4—C5	0.6 (3)	C8—C9—C14—C13	−179.2 (2)
C7—C3—C4—C5	−179.4 (2)	C13—O2—C15—C16	−178.7 (3)
C1—N—C5—C4	−0.9 (3)	O5—S—C17—C18	−19.3 (2)
C6—N—C5—C4	176.9 (2)	O4—S—C17—C18	106.6 (2)
C3—C4—C5—N	0.3 (4)	O3—S—C17—C18	−136.8 (2)
C4—C3—C7—C8	175.4 (2)	O5—S—C17—C22	158.9 (2)
C2—C3—C7—C8	−4.7 (4)	O4—S—C17—C22	−75.3 (2)
C3—C7—C8—C9	−179.7 (2)	O3—S—C17—C22	41.4 (2)
C7—C8—C9—C10	−175.9 (2)	C22—C17—C18—C19	−0.6 (4)
C7—C8—C9—C14	3.5 (4)	S—C17—C18—C19	177.6 (2)
C14—C9—C10—C11	−1.4 (4)	C17—C18—C19—C20	−0.2 (4)
C8—C9—C10—C11	178.0 (2)	C18—C19—C20—C21	1.2 (4)
C9—C10—C11—C12	1.1 (4)	C18—C19—C20—C23	−177.1 (3)
C10—C11—C12—O1	−179.3 (2)	C19—C20—C21—C22	−1.3 (4)
C10—C11—C12—C13	0.4 (4)	C23—C20—C21—C22	176.9 (3)
C15—O2—C13—C14	1.6 (4)	C20—C21—C22—C17	0.6 (4)
C15—O2—C13—C12	−179.0 (2)	C18—C17—C22—C21	0.4 (4)
O1—C12—C13—O2	−1.3 (3)	S—C17—C22—C21	−177.75 (18)
C11—C12—C13—O2	179.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O6i	0.82	1.82	2.632 (3)	170
O6—H6OB···O3	0.85 (1)	2.36 (2)	2.692 (3)	104 (2)
O6—H6OA···O5ii	0.86 (3)	1.98 (3)	2.832 (4)	169 (3)
C4—H4···O4	0.93	2.53	3.426 (3)	161
C5—H5···O1iii	0.93	2.59	3.217 (3)	125

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O6i	0.82	1.82	2.632 (3)	170
O6—H6OB⋯O3	0.85 (1)	2.36 (2)	2.692 (3)	103.9 (19)
O6—H6OA⋯O5ii	0.86 (3)	1.98 (3)	2.832 (4)	169 (3)
C4—H4⋯O4	0.93	2.53	3.426 (3)	161
C5—H5⋯O1iii	0.93	2.59	3.217 (3)	125

Symmetry codes: (i) ; (ii) ; (iii) .