(2Z)-3-(4-Hydroxy­phen­yl)-2-(pyridinium-4-yl)acrylonitrile p-toluene­sulfonate

In the structure of the title compound, C₁₅H₁₃N₂O⁺·C₇H₇O₃S⁻, the cation has a Z geometry about the ethyl­ene bridge that links the heterocyclic and aromatic rings. The skeleton of the cation is slightly non-planar; the dihedral angles between the ethyl­ene linkage and the pyridinium ring and p-hydroxy­phenyl ring are 9.2 (1) and 2.0 (1)°, respectively. In the crystal structure, the cations are stacked along the b axis, with a head-to-tail orientation, and weak inter­molecular C—H...N hydrogen bonds link the cations into chains along the a axis. In addition, inter­molecular O—H...O and C—H...O hydrogen bonds between cations and anions link two such chains together with a mean inter­planar distance of 3.23 Å between cations.

Key indicators

• Single-crystal X-ray study
• T = 213 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.056
• wR factor = 0.170
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         S1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.05
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C7     ...       1.44 Ang.

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

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

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Computing details

Data collection: SMART APEX (Bruker, 2003); cell refinement: SAINT-Plus-NT (Bruker, 2001); data reduction: SAINT-Plus-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Sheldrick, 2001); software used to prepare material for publication: SHELXL97.

(2Z)-3-(4-Hydroxyphenyl)-2-(pyridinium-4-yl)acrylonitrile p-toluenesulfonate

Crystal data

C15H13N2O^+·C7H7O3S^−	Z = 2
Mr = 408.47	F(000) = 428
Triclinic, P1	Dx = 1.387 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9959 (15) Å	Cell parameters from 217 reflections
b = 7.4103 (16) Å	θ = 4–26°
c = 21.343 (5) Å	µ = 0.20 mm^−1
α = 84.138 (3)°	T = 213 K
β = 85.684 (3)°	Prism, yellow
γ = 62.749 (2)°	0.45 × 0.35 × 0.20 mm
V = 978.0 (4) Å^3

Data collection

Bruker SMART CCD diffractometer	3792 independent reflections
Radiation source: fine-focus sealed tube	2891 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
φ and ω scans	θmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
Tmin = 0.925, Tmax = 0.962	k = −9→8
6597 measured reflections	l = −26→26

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.1088P)^2 + 0.3P] where P = (Fo^2 + 2Fc^2)/3
3792 reflections	(Δ/σ)max < 0.001
268 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Experimental. The key features in the NMR spectra were the following: ¹H (300 MHz, DMSO-d₆) δ 10.94 (s, OH), 8.96 (d, 2H), 8.60 (s, 1H), 8.33 (d, 2H), 8.07 (d, 2H), 7.47 (d, 2H), 7.11 (d, 2H), 7.02 (d, 2H), 4.30 (s, 3H), 2.28 (s, 3H); ¹³C (75 MHz, DMSO-d₆) δ 162.91, 151.37, 149.65, 145.66, 145.49, 137.65, 133.82, 128.06, 125.47, 123.62, 122.23, 116.92, 116.58, 100.10, 47.05, 20.74.

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. All C-bound H atoms were placed in geometrically calculated positions and refined using a riding model with C—H distances of 0.94 Å for aromatic and ethylene H atoms, 0.97 Å for CH₃ groups. H-atom of HO group was refined isotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.8703 (4)	0.4138 (4)	0.27887 (9)	0.0522 (6)
N1	0.8223 (4)	0.0771 (3)	0.77669 (10)	0.0372 (5)
N2	1.3566 (4)	0.1633 (4)	0.56885 (11)	0.0464 (6)
C1	1.1850 (4)	0.1817 (4)	0.57527 (12)	0.0347 (6)
C2	0.9982 (4)	0.1017 (4)	0.76182 (13)	0.0408 (6)
H2A	1.0891	0.0902	0.7939	0.049*
C3	1.0476 (4)	0.1432 (4)	0.70098 (12)	0.0396 (6)
H3A	1.1724	0.1596	0.6917	0.048*
C4	0.9175 (4)	0.1617 (4)	0.65237 (12)	0.0312 (5)
C5	0.7326 (4)	0.1374 (4)	0.67007 (12)	0.0375 (6)
H5A	0.6375	0.1501	0.6391	0.045*
C6	0.6901 (5)	0.0958 (4)	0.73119 (12)	0.0405 (6)
H6A	0.5658	0.0796	0.7421	0.049*
C7	0.9714 (4)	0.2001 (4)	0.58658 (12)	0.0315 (5)
C8	0.8357 (4)	0.2438 (4)	0.53893 (12)	0.0309 (5)
H8A	0.7033	0.2462	0.5521	0.037*
C9	0.8549 (4)	0.2872 (4)	0.47211 (11)	0.0308 (5)
C10	1.0327 (4)	0.2961 (4)	0.43961 (12)	0.0361 (6)
H10A	1.1537	0.2718	0.4621	0.043*
C11	1.0331 (4)	0.3393 (4)	0.37594 (12)	0.0386 (6)
H11A	1.1533	0.3463	0.3553	0.046*
C12	0.8578 (4)	0.3731 (4)	0.34120 (12)	0.0367 (6)
C13	0.6821 (4)	0.3599 (4)	0.37207 (12)	0.0367 (6)
H13A	0.5640	0.3791	0.3490	0.044*
C14	0.6812 (4)	0.3189 (4)	0.43598 (12)	0.0333 (6)
H14A	0.5606	0.3119	0.4563	0.040*
C15	0.7742 (5)	0.0285 (5)	0.84279 (12)	0.0484 (7)
H15A	0.9063	−0.0684	0.8628	0.073*
H15B	0.6749	−0.0301	0.8442	0.073*
H15C	0.7096	0.1519	0.8649	0.073*
S1	0.53836 (11)	0.33230 (11)	0.17705 (3)	0.0413 (2)
O2	0.5449 (4)	0.4846 (4)	0.21335 (12)	0.0732 (8)
O3	0.5030 (5)	0.1829 (5)	0.21529 (15)	0.0985 (11)
O4	0.7242 (4)	0.2523 (4)	0.13533 (11)	0.0730 (8)
C16	0.3131 (4)	0.4693 (4)	0.12920 (12)	0.0347 (6)
C17	0.3379 (5)	0.5531 (4)	0.07046 (12)	0.0405 (6)
H17A	0.4755	0.5317	0.0550	0.049*
C18	0.1607 (5)	0.6684 (4)	0.03431 (13)	0.0441 (7)
H18A	0.1790	0.7247	−0.0058	0.053*
C19	−0.0423 (5)	0.7025 (4)	0.05591 (14)	0.0430 (7)
C20	−0.0643 (5)	0.6151 (5)	0.11483 (14)	0.0468 (7)
H20A	−0.2017	0.6350	0.1300	0.056*
C21	0.1119 (5)	0.4989 (4)	0.15177 (13)	0.0420 (6)
H21A	0.0944	0.4409	0.1917	0.050*
C22	−0.2365 (6)	0.8305 (6)	0.01742 (18)	0.0649 (9)
H22A	−0.1947	0.8243	−0.0270	0.097*
H22B	−0.2983	0.9705	0.0284	0.097*
H22C	−0.3420	0.7796	0.0260	0.097*
H1A	0.751 (8)	0.440 (7)	0.262 (2)	0.108 (17)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0534 (13)	0.0831 (16)	0.0317 (10)	−0.0420 (13)	−0.0045 (9)	0.0031 (10)
N1	0.0421 (13)	0.0326 (12)	0.0323 (11)	−0.0125 (10)	−0.0071 (10)	−0.0005 (9)
N2	0.0338 (13)	0.0605 (16)	0.0471 (13)	−0.0229 (12)	−0.0047 (10)	−0.0035 (11)
C1	0.0332 (14)	0.0385 (14)	0.0335 (13)	−0.0168 (12)	−0.0066 (10)	−0.0008 (11)
C2	0.0374 (15)	0.0425 (16)	0.0397 (14)	−0.0144 (13)	−0.0135 (12)	−0.0015 (12)
C3	0.0343 (14)	0.0454 (16)	0.0410 (14)	−0.0191 (12)	−0.0100 (11)	0.0006 (12)
C4	0.0271 (12)	0.0263 (12)	0.0368 (13)	−0.0084 (10)	−0.0062 (10)	−0.0028 (10)
C5	0.0352 (14)	0.0464 (16)	0.0343 (13)	−0.0209 (12)	−0.0089 (11)	0.0005 (11)
C6	0.0380 (15)	0.0481 (16)	0.0380 (14)	−0.0220 (13)	−0.0066 (11)	0.0019 (12)
C7	0.0290 (13)	0.0289 (12)	0.0368 (13)	−0.0128 (10)	−0.0047 (10)	−0.0027 (10)
C8	0.0254 (12)	0.0320 (13)	0.0365 (13)	−0.0140 (10)	−0.0025 (10)	−0.0015 (10)
C9	0.0292 (13)	0.0281 (12)	0.0353 (13)	−0.0127 (10)	−0.0050 (10)	−0.0016 (10)
C10	0.0298 (13)	0.0439 (15)	0.0397 (14)	−0.0206 (12)	−0.0052 (11)	−0.0029 (11)
C11	0.0359 (14)	0.0472 (16)	0.0376 (14)	−0.0232 (13)	0.0006 (11)	−0.0037 (12)
C12	0.0421 (15)	0.0378 (14)	0.0324 (13)	−0.0196 (12)	−0.0033 (11)	−0.0030 (11)
C13	0.0323 (14)	0.0393 (15)	0.0400 (14)	−0.0166 (12)	−0.0087 (11)	−0.0018 (11)
C14	0.0259 (12)	0.0343 (13)	0.0404 (14)	−0.0141 (11)	−0.0028 (10)	−0.0018 (11)
C15	0.0589 (19)	0.0524 (18)	0.0290 (13)	−0.0212 (15)	−0.0048 (13)	0.0003 (12)
S1	0.0378 (4)	0.0421 (4)	0.0414 (4)	−0.0162 (3)	−0.0124 (3)	0.0064 (3)
O2	0.0700 (16)	0.0632 (15)	0.0739 (16)	−0.0123 (12)	−0.0391 (13)	−0.0141 (13)
O3	0.0766 (18)	0.107 (2)	0.123 (2)	−0.0605 (17)	−0.0576 (17)	0.0789 (19)
O4	0.0407 (13)	0.0874 (18)	0.0582 (14)	−0.0007 (12)	−0.0066 (11)	−0.0024 (13)
C16	0.0347 (14)	0.0336 (13)	0.0356 (13)	−0.0153 (11)	−0.0083 (11)	0.0016 (11)
C17	0.0374 (15)	0.0477 (16)	0.0351 (13)	−0.0188 (13)	−0.0024 (11)	−0.0002 (12)
C18	0.0485 (17)	0.0498 (17)	0.0343 (13)	−0.0233 (14)	−0.0081 (12)	0.0050 (12)
C19	0.0398 (16)	0.0369 (15)	0.0476 (15)	−0.0120 (12)	−0.0141 (12)	−0.0003 (12)
C20	0.0333 (15)	0.0470 (17)	0.0572 (17)	−0.0169 (13)	−0.0050 (13)	0.0036 (14)
C21	0.0405 (15)	0.0421 (15)	0.0415 (14)	−0.0187 (13)	−0.0025 (12)	0.0048 (12)
C22	0.054 (2)	0.059 (2)	0.076 (2)	−0.0191 (17)	−0.0309 (18)	0.0104 (18)

Geometric parameters (Å, º)

O1—C12	1.339 (3)	C12—C13	1.389 (4)
O1—H1A	0.86 (5)	C13—C14	1.367 (4)
N1—C2	1.335 (4)	C13—H13A	0.9400
N1—C6	1.344 (3)	C14—H14A	0.9400
N1—C15	1.473 (3)	C15—H15A	0.9700
N2—C1	1.144 (3)	C15—H15B	0.9700
C1—C7	1.441 (3)	C15—H15C	0.9700
C2—C3	1.360 (4)	S1—O3	1.410 (2)
C2—H2A	0.9400	S1—O4	1.436 (2)
C3—C4	1.386 (4)	S1—O2	1.452 (2)
C3—H3A	0.9400	S1—C16	1.767 (3)
C4—C5	1.405 (4)	C16—C17	1.376 (4)
C4—C7	1.460 (3)	C16—C21	1.378 (4)
C5—C6	1.352 (4)	C17—C18	1.379 (4)
C5—H5A	0.9400	C17—H17A	0.9400
C6—H6A	0.9400	C18—C19	1.375 (4)
C7—C8	1.355 (3)	C18—H18A	0.9400
C8—C9	1.440 (3)	C19—C20	1.386 (4)
C8—H8A	0.9400	C19—C22	1.500 (4)
C9—C14	1.403 (3)	C20—C21	1.385 (4)
C9—C10	1.403 (3)	C20—H20A	0.9400
C10—C11	1.364 (4)	C21—H21A	0.9400
C10—H10A	0.9400	C22—H22A	0.9700
C11—C12	1.391 (4)	C22—H22B	0.9700
C11—H11A	0.9400	C22—H22C	0.9700
C12—O1—H1A	110 (3)	C12—C13—H13A	120.1
C2—N1—C6	119.9 (2)	C13—C14—C9	122.0 (2)
C2—N1—C15	119.9 (2)	C13—C14—H14A	119.0
C6—N1—C15	120.2 (2)	C9—C14—H14A	119.0
N2—C1—C7	177.1 (3)	N1—C15—H15A	109.5
N1—C2—C3	120.9 (2)	N1—C15—H15B	109.5
N1—C2—H2A	119.5	H15A—C15—H15B	109.5
C3—C2—H2A	119.5	N1—C15—H15C	109.5
C2—C3—C4	121.3 (2)	H15A—C15—H15C	109.5
C2—C3—H3A	119.3	H15B—C15—H15C	109.5
C4—C3—H3A	119.3	O3—S1—O4	114.4 (2)
C3—C4—C5	116.0 (2)	O3—S1—O2	112.5 (2)
C3—C4—C7	122.1 (2)	O4—S1—O2	110.10 (17)
C5—C4—C7	121.9 (2)	O3—S1—C16	107.81 (13)
C6—C5—C4	120.7 (2)	O4—S1—C16	106.81 (13)
C6—C5—H5A	119.7	O2—S1—C16	104.52 (13)
C4—C5—H5A	119.7	C17—C16—C21	120.2 (2)
N1—C6—C5	121.2 (2)	C17—C16—S1	119.9 (2)
N1—C6—H6A	119.4	C21—C16—S1	119.9 (2)
C5—C6—H6A	119.4	C16—C17—C18	119.9 (3)
C8—C7—C1	121.7 (2)	C16—C17—H17A	120.0
C8—C7—C4	123.4 (2)	C18—C17—H17A	120.0
C1—C7—C4	114.8 (2)	C19—C18—C17	121.2 (2)
C7—C8—C9	132.5 (2)	C19—C18—H18A	119.4
C7—C8—H8A	113.7	C17—C18—H18A	119.4
C9—C8—H8A	113.7	C18—C19—C20	118.2 (3)
C14—C9—C10	117.0 (2)	C18—C19—C22	121.6 (3)
C14—C9—C8	116.8 (2)	C20—C19—C22	120.2 (3)
C10—C9—C8	126.1 (2)	C21—C20—C19	121.4 (3)
C11—C10—C9	121.1 (2)	C21—C20—H20A	119.3
C11—C10—H10A	119.4	C19—C20—H20A	119.3
C9—C10—H10A	119.4	C16—C21—C20	119.1 (3)
C10—C11—C12	120.8 (2)	C16—C21—H21A	120.4
C10—C11—H11A	119.6	C20—C21—H21A	120.4
C12—C11—H11A	119.6	C19—C22—H22A	109.5
O1—C12—C13	123.5 (2)	C19—C22—H22B	109.5
O1—C12—C11	117.4 (2)	H22A—C22—H22B	109.5
C13—C12—C11	119.1 (2)	C19—C22—H22C	109.5
C14—C13—C12	119.9 (2)	H22A—C22—H22C	109.5
C14—C13—H13A	120.1	H22B—C22—H22C	109.5
C6—N1—C2—C3	−0.8 (4)	C10—C11—C12—C13	−0.8 (4)
C15—N1—C2—C3	178.9 (3)	O1—C12—C13—C14	−179.6 (3)
N1—C2—C3—C4	0.1 (4)	C11—C12—C13—C14	1.5 (4)
C2—C3—C4—C5	0.7 (4)	C12—C13—C14—C9	−0.7 (4)
C2—C3—C4—C7	−178.1 (2)	C10—C9—C14—C13	−1.0 (4)
C3—C4—C5—C6	−0.8 (4)	C8—C9—C14—C13	−179.5 (2)
C7—C4—C5—C6	177.9 (2)	O3—S1—C16—C17	−150.1 (3)
C2—N1—C6—C5	0.7 (4)	O4—S1—C16—C17	−26.7 (3)
C15—N1—C6—C5	−179.0 (3)	O2—S1—C16—C17	90.0 (3)
C4—C5—C6—N1	0.2 (4)	O3—S1—C16—C21	32.5 (3)
C3—C4—C7—C8	−171.6 (2)	O4—S1—C16—C21	155.9 (2)
C5—C4—C7—C8	9.7 (4)	O2—S1—C16—C21	−87.4 (2)
C3—C4—C7—C1	10.3 (4)	C21—C16—C17—C18	0.6 (4)
C5—C4—C7—C1	−168.4 (2)	S1—C16—C17—C18	−176.9 (2)
C1—C7—C8—C9	−2.5 (4)	C16—C17—C18—C19	0.2 (4)
C4—C7—C8—C9	179.5 (2)	C17—C18—C19—C20	−1.0 (4)
C7—C8—C9—C14	177.7 (3)	C17—C18—C19—C22	179.0 (3)
C7—C8—C9—C10	−0.7 (5)	C18—C19—C20—C21	1.0 (5)
C14—C9—C10—C11	1.7 (4)	C22—C19—C20—C21	−178.9 (3)
C8—C9—C10—C11	−179.8 (2)	C17—C16—C21—C20	−0.6 (4)
C9—C10—C11—C12	−0.9 (4)	S1—C16—C21—C20	176.9 (2)
C10—C11—C12—O1	−179.7 (3)	C19—C20—C21—C16	−0.2 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.86 (5)	1.73 (5)	2.578 (3)	167 (3)
C5—H5A···N2^i	0.94	2.52	3.454 (4)	172
C6—H6A···O3^ii	0.94	2.30	3.039 (4)	136
C21—H21A···O1^i	0.94	2.39	3.248 (4)	151

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