2-(4-Hydroxy­styryl)-1-methyl­pyridinium 4-bromo­benzene­sulfonate

Chantrapromma, S.; Ruanwas, P.; Fun, H.-K.; Patil, P.S.

doi:10.1107/S1600536806046137

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2-(4-Hydroxystyryl)-1-methylpyridinium 4-bromobenzenesulfonate

S. Chantrapromma, P. Ruanwas, H.-K. Fun and P. S. Patil

The title compound, C₁₄H₁₄NO⁺·C₆H₄BrSO₃⁻, (I), crystallizes in a non-centrosymmetric space group and exhibits non-linear optical properties. The second-harmonic generation (SHG) effect of (I) is about 0.14 times that of urea. The cation is almost planar and exists in an E configuration. The pyridinium and benzene rings of the cation make a dihedral angle of 4.52 (8)°. The dihedral angles between the benzene ring of the anion and the mean planes through the pyridinium and benzene rings of the cation are 67.06 (8) and 71.56 (8)°, respectively. In the crystal structure, the cations and anions are linked by O—H

O hydrogen bonds and weak C—H

O interactions into a three-dimensional network. C—H

π interactions are also observed in the crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806046137/wn2084sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536806046137/wn2084Isup2.hkl Contains datablock I

CCDC reference: 630504

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.003 Å
R factor = 0.024
wR factor = 0.058
Data-to-parameter ratio = 21.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.91
PLAT354_ALERT_3_C Short   O-H Bond (0.82A)   O4     -   H1O4   ...       0.71 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C14 H14 N O

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.914
            Tmax scaled      0.477 Tmin scaled      0.360
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           29.99
           From the CIF: _reflns_number_total               5286
           Count of symmetry unique reflns         2740
           Completeness (_total/calc)            192.92%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      2546
           Fraction of Friedel pairs measured     0.929
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Computing details top

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).

2-(4-Hydroxystyryl)-1-methylpyridinium 4-bromobenzenesulfonate top

Crystal data top

C₁₄H₁₄NO⁺·C₆H₄BrO₃S⁻	F(000) = 456
M_r = 448.32	D_x = 1.625 Mg m⁻³
Monoclinic, P2₁	Melting point = 513–516 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 6.2827 (1) Å	Cell parameters from 5107 reflections
b = 19.5377 (3) Å	θ = 2.1–30.0°
c = 7.5025 (1) Å	µ = 2.39 mm⁻¹
β = 95.923 (1)°	T = 100 K
V = 916.01 (2) Å³	Block, purple
Z = 2	0.48 × 0.39 × 0.31 mm

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	5286 independent reflections
Radiation source: fine-focus sealed tube	5107 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 8.33 pixels mm^-1	θ_max = 30.0°, θ_min = 2.1°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −27→27
T_min = 0.394, T_max = 0.522	l = −10→10
15947 measured 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)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.024P)² + 0.0214P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
5286 reflections	Δρ_max = 0.60 e Å⁻³
249 parameters	Δρ_min = −0.43 e Å⁻³
1 restraint	Absolute structure: Flack (1983), with 2427 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.013 (4)

Special details top

Experimental. The data were collected with the Oxford Cyrosystem 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
Br1	−0.35458 (2)	0.542441 (10)	0.88108 (2)	0.02165 (5)
S1	0.21574 (6)	0.63716 (2)	0.25977 (6)	0.01564 (8)
N1	1.6968 (2)	0.80144 (7)	0.9335 (2)	0.0175 (3)
O1	0.3676 (2)	0.68651 (6)	0.34852 (19)	0.0234 (3)
O2	0.3201 (2)	0.57579 (7)	0.20216 (18)	0.0217 (3)
O3	0.0701 (2)	0.66804 (7)	0.11896 (19)	0.0223 (3)
O4	0.4342 (2)	0.81972 (7)	0.28717 (19)	0.0209 (3)
H1O4	0.405 (4)	0.7851 (15)	0.298 (4)	0.029 (7)*
C1	−0.1844 (3)	0.56807 (9)	0.6963 (2)	0.0175 (3)
C2	−0.2764 (3)	0.56796 (9)	0.5205 (2)	0.0184 (3)
H2A	−0.4171	0.5536	0.4926	0.022*
C3	−0.1547 (3)	0.58972 (9)	0.3859 (2)	0.0166 (3)
H3A	−0.2141	0.5903	0.2671	0.020*
C4	0.0568 (3)	0.61062 (8)	0.4299 (2)	0.0154 (3)
C5	0.1465 (3)	0.60958 (9)	0.6078 (2)	0.0178 (3)
H5A	0.2878	0.6231	0.6361	0.021*
C6	0.0262 (3)	0.58846 (9)	0.7433 (2)	0.0189 (3)
H6A	0.0849	0.5880	0.8623	0.023*
C7	1.8901 (3)	0.81452 (10)	1.0241 (2)	0.0192 (3)
H7A	1.9699	0.7785	1.0771	0.023*
C8	1.9713 (3)	0.87979 (10)	1.0397 (2)	0.0198 (3)
H8A	2.1038	0.8882	1.1031	0.024*
C9	1.8506 (3)	0.93288 (9)	0.9583 (3)	0.0196 (3)
H9A	1.9024	0.9775	0.9656	0.024*
C10	1.6532 (3)	0.91912 (9)	0.8664 (2)	0.0181 (3)
H10A	1.5725	0.9549	0.8128	0.022*
C11	1.5726 (3)	0.85258 (9)	0.8525 (2)	0.0167 (3)
C12	1.3673 (3)	0.83454 (9)	0.7565 (3)	0.0197 (3)
H12	1.3236	0.7892	0.7610	0.024*
C13	1.2360 (3)	0.87866 (9)	0.6615 (2)	0.0183 (3)
H13A	1.2800	0.9241	0.6580	0.022*
C14	1.0309 (3)	0.86125 (9)	0.5639 (2)	0.0164 (3)
C15	0.9595 (3)	0.79371 (9)	0.5400 (3)	0.0193 (3)
H15A	1.0471	0.7581	0.5855	0.023*
C16	0.7613 (3)	0.77873 (9)	0.4500 (3)	0.0194 (3)
H16A	0.7166	0.7335	0.4367	0.023*
C17	0.6283 (3)	0.83165 (9)	0.3792 (2)	0.0169 (3)
C18	0.6970 (3)	0.89946 (9)	0.4000 (2)	0.0180 (3)
H18A	0.6094	0.9350	0.3540	0.022*
C19	0.8956 (3)	0.91351 (9)	0.4894 (2)	0.0181 (3)
H19A	0.9412	0.9587	0.5005	0.022*
C20	1.6250 (3)	0.72959 (10)	0.9224 (3)	0.0246 (4)
H20A	1.7329	0.7008	0.9835	0.037*
H20B	1.6009	0.7161	0.7989	0.037*
H20C	1.4944	0.7251	0.9775	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02040 (8)	0.02600 (8)	0.01847 (8)	−0.00373 (7)	0.00163 (5)	0.00159 (8)
S1	0.01578 (17)	0.01394 (16)	0.01682 (19)	−0.00035 (14)	−0.00011 (14)	0.00063 (14)
N1	0.0167 (6)	0.0156 (7)	0.0198 (7)	0.0013 (5)	0.0009 (5)	0.0015 (5)
O1	0.0242 (7)	0.0198 (6)	0.0254 (7)	−0.0075 (5)	−0.0016 (5)	0.0013 (5)
O2	0.0214 (6)	0.0205 (6)	0.0235 (7)	0.0033 (5)	0.0042 (5)	0.0006 (5)
O3	0.0220 (6)	0.0232 (6)	0.0212 (7)	0.0032 (5)	−0.0011 (5)	0.0045 (5)
O4	0.0163 (6)	0.0207 (7)	0.0244 (7)	−0.0017 (5)	−0.0033 (5)	0.0015 (5)
C1	0.0204 (8)	0.0148 (7)	0.0177 (8)	0.0002 (6)	0.0033 (6)	0.0008 (6)
C2	0.0147 (7)	0.0179 (7)	0.0221 (9)	0.0012 (6)	−0.0005 (6)	−0.0009 (6)
C3	0.0169 (7)	0.0173 (7)	0.0147 (8)	0.0013 (6)	−0.0021 (6)	0.0000 (6)
C4	0.0161 (7)	0.0130 (6)	0.0169 (8)	0.0007 (6)	0.0010 (6)	−0.0016 (6)
C5	0.0149 (8)	0.0177 (7)	0.0199 (9)	−0.0017 (6)	−0.0023 (6)	−0.0015 (6)
C6	0.0205 (8)	0.0190 (7)	0.0164 (8)	−0.0003 (6)	−0.0021 (6)	−0.0011 (6)
C7	0.0166 (8)	0.0238 (8)	0.0170 (8)	0.0026 (6)	0.0007 (6)	0.0021 (6)
C8	0.0170 (8)	0.0260 (8)	0.0162 (8)	−0.0004 (6)	0.0011 (6)	−0.0022 (6)
C9	0.0177 (8)	0.0186 (8)	0.0220 (9)	−0.0014 (6)	0.0001 (6)	−0.0013 (6)
C10	0.0170 (8)	0.0168 (7)	0.0204 (9)	0.0007 (6)	0.0014 (6)	0.0005 (6)
C11	0.0141 (7)	0.0185 (8)	0.0179 (8)	0.0025 (6)	0.0031 (6)	0.0005 (6)
C12	0.0169 (8)	0.0169 (7)	0.0247 (9)	0.0000 (6)	−0.0007 (7)	0.0003 (7)
C13	0.0163 (7)	0.0166 (7)	0.0216 (9)	−0.0013 (6)	0.0006 (6)	−0.0011 (6)
C14	0.0139 (7)	0.0188 (7)	0.0164 (8)	0.0001 (6)	0.0015 (6)	0.0001 (6)
C15	0.0166 (8)	0.0156 (7)	0.0255 (10)	0.0031 (6)	0.0004 (6)	0.0006 (7)
C16	0.0186 (8)	0.0146 (7)	0.0246 (9)	−0.0008 (6)	0.0003 (7)	−0.0008 (6)
C17	0.0157 (8)	0.0182 (8)	0.0168 (8)	−0.0009 (6)	0.0026 (6)	0.0005 (6)
C18	0.0192 (7)	0.0164 (7)	0.0181 (8)	0.0020 (6)	0.0002 (6)	0.0013 (6)
C19	0.0185 (8)	0.0147 (7)	0.0211 (9)	0.0011 (6)	0.0015 (6)	0.0009 (6)
C20	0.0228 (9)	0.0165 (8)	0.0334 (10)	−0.0003 (7)	−0.0023 (7)	0.0039 (7)

Geometric parameters (Å, º) top

Br1—C1	1.9034 (17)	C8—H8A	0.9300
S1—O2	1.4535 (13)	C9—C10	1.382 (2)
S1—O3	1.4551 (14)	C9—H9A	0.9300
S1—O1	1.4671 (13)	C10—C11	1.395 (2)
S1—C4	1.7771 (18)	C10—H10A	0.9300
N1—C7	1.354 (2)	C11—C12	1.455 (2)
N1—C11	1.370 (2)	C12—C13	1.345 (2)
N1—C20	1.474 (2)	C12—H12	0.9300
O4—C17	1.358 (2)	C13—C14	1.456 (2)
O4—H1O4	0.71 (3)	C13—H13A	0.9300
C1—C2	1.384 (3)	C14—C15	1.399 (2)
C1—C6	1.392 (3)	C14—C19	1.407 (2)
C2—C3	1.394 (2)	C15—C16	1.385 (3)
C2—H2A	0.9300	C15—H15A	0.9300
C3—C4	1.397 (2)	C16—C17	1.399 (2)
C3—H3A	0.9300	C16—H16A	0.9300
C4—C5	1.394 (2)	C17—C18	1.397 (2)
C5—C6	1.391 (3)	C18—C19	1.382 (2)
C5—H5A	0.9300	C18—H18A	0.9300
C6—H6A	0.9300	C19—H19A	0.9300
C7—C8	1.374 (3)	C20—H20A	0.9600
C7—H7A	0.9300	C20—H20B	0.9600
C8—C9	1.389 (3)	C20—H20C	0.9600

O2—S1—O3	113.28 (8)	C9—C10—C11	121.22 (17)
O2—S1—O1	112.64 (8)	C9—C10—H10A	119.4
O3—S1—O1	112.81 (8)	C11—C10—H10A	119.4
O2—S1—C4	106.08 (8)	N1—C11—C10	117.45 (16)
O3—S1—C4	106.54 (8)	N1—C11—C12	118.56 (15)
O1—S1—C4	104.66 (8)	C10—C11—C12	123.98 (16)
C7—N1—C11	121.68 (15)	C13—C12—C11	124.82 (16)
C7—N1—C20	117.49 (15)	C13—C12—H12	117.6
C11—N1—C20	120.82 (15)	C11—C12—H12	117.6
C17—O4—H1O4	109 (2)	C12—C13—C14	125.41 (16)
C2—C1—C6	122.33 (16)	C12—C13—H13A	117.3
C2—C1—Br1	118.88 (13)	C14—C13—H13A	117.3
C6—C1—Br1	118.76 (14)	C15—C14—C19	117.44 (16)
C1—C2—C3	118.88 (16)	C15—C14—C13	122.71 (16)
C1—C2—H2A	120.6	C19—C14—C13	119.85 (15)
C3—C2—H2A	120.6	C16—C15—C14	121.46 (16)
C2—C3—C4	119.84 (16)	C16—C15—H15A	119.3
C2—C3—H3A	120.1	C14—C15—H15A	119.3
C4—C3—H3A	120.1	C15—C16—C17	120.03 (16)
C5—C4—C3	120.16 (16)	C15—C16—H16A	120.0
C5—C4—S1	119.37 (13)	C17—C16—H16A	120.0
C3—C4—S1	120.46 (13)	O4—C17—C18	118.07 (16)
C6—C5—C4	120.53 (16)	O4—C17—C16	122.40 (16)
C6—C5—H5A	119.7	C18—C17—C16	119.53 (16)
C4—C5—H5A	119.7	C19—C18—C17	119.72 (16)
C5—C6—C1	118.26 (17)	C19—C18—H18A	120.1
C5—C6—H6A	120.9	C17—C18—H18A	120.1
C1—C6—H6A	120.9	C18—C19—C14	121.80 (16)
N1—C7—C8	121.61 (17)	C18—C19—H19A	119.1
N1—C7—H7A	119.2	C14—C19—H19A	119.1
C8—C7—H7A	119.2	N1—C20—H20A	109.5
C7—C8—C9	118.32 (17)	N1—C20—H20B	109.5
C7—C8—H8A	120.8	H20A—C20—H20B	109.5
C9—C8—H8A	120.8	N1—C20—H20C	109.5
C10—C9—C8	119.71 (17)	H20A—C20—H20C	109.5
C10—C9—H9A	120.1	H20B—C20—H20C	109.5
C8—C9—H9A	120.1

C6—C1—C2—C3	−0.7 (3)	C7—N1—C11—C10	0.1 (3)
Br1—C1—C2—C3	177.11 (12)	C20—N1—C11—C10	−178.91 (16)
C1—C2—C3—C4	0.5 (2)	C7—N1—C11—C12	179.58 (16)
C2—C3—C4—C5	0.2 (2)	C20—N1—C11—C12	0.5 (2)
C2—C3—C4—S1	178.96 (13)	C9—C10—C11—N1	0.0 (3)
O2—S1—C4—C5	89.10 (15)	C9—C10—C11—C12	−179.40 (16)
O3—S1—C4—C5	−149.93 (14)	N1—C11—C12—C13	−175.52 (17)
O1—S1—C4—C5	−30.21 (16)	C10—C11—C12—C13	3.9 (3)
O2—S1—C4—C3	−89.68 (14)	C11—C12—C13—C14	179.58 (17)
O3—S1—C4—C3	31.29 (15)	C12—C13—C14—C15	−8.3 (3)
O1—S1—C4—C3	151.01 (13)	C12—C13—C14—C19	171.64 (18)
C3—C4—C5—C6	−0.7 (2)	C19—C14—C15—C16	−1.5 (3)
S1—C4—C5—C6	−179.44 (13)	C13—C14—C15—C16	178.47 (17)
C4—C5—C6—C1	0.5 (3)	C14—C15—C16—C17	0.6 (3)
C2—C1—C6—C5	0.2 (3)	C15—C16—C17—O4	178.80 (16)
Br1—C1—C6—C5	−177.57 (13)	C15—C16—C17—C18	0.0 (3)
C11—N1—C7—C8	0.1 (3)	O4—C17—C18—C19	−178.53 (15)
C20—N1—C7—C8	179.22 (17)	C16—C17—C18—C19	0.3 (3)
N1—C7—C8—C9	−0.6 (3)	C17—C18—C19—C14	−1.3 (3)
C7—C8—C9—C10	0.7 (3)	C15—C14—C19—C18	1.8 (3)
C8—C9—C10—C11	−0.4 (3)	C13—C14—C19—C18	−178.13 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H1O4···O1	0.71 (3)	1.98 (3)	2.6833 (18)	171 (3)
C5—H5A···O1	0.93	2.58	2.921 (2)	102
C6—H6A···O3ⁱ	0.93	2.49	3.206 (2)	134
C7—H7A···O3ⁱⁱ	0.93	2.26	3.132 (2)	156
C10—H10A···O2ⁱⁱⁱ	0.93	2.46	3.111 (2)	127
C16—H16A···O1	0.93	2.41	3.091 (2)	130
C20—H20A···O3ⁱⁱ	0.96	2.34	3.254 (2)	158
C16—H16A···Cg1^iv	0.93	3.24	3.9330 (19)	133
C19—H19A···Cg1^v	0.93	2.72	3.6245 (19)	165

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

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