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The crystal structure of 4-(4-di­methyl­amino­phenyl­ethenyl)­pyridine N-oxide, C15H16N2O, has been determined from X-ray laboratory powder diffraction data. The powder pattern was indexed with a monoclinic unit cell with a long a axis. The structure was solved by a grid search technique. The subsequent bond-restrained Rietveld refinement gave bond lengths and angles within expected ranges.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012340/cf6258sup1.cif
Contains datablocks I, global

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S1600536803012340/cf6258Isup2.rtv
Contains datablock I

CCDC reference: 217599

Key indicators

  • Powder X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.090 Å
  • R factor = 0.000
  • wR factor = 0.000
  • Data-to-parameter ratio = 0.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
REFLT_03 _reflns_number_total not in the CIF REFNR_01 Alert A Ratio of reflections to parameters is < 6 for a centrosymmetric structure sine(theta)/lambda 0.3246 Proportion of unique data used NaN Ratio reflections to parameters 0.0000 THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.3246
Yellow Alert Alert Level C:
RADNW_01 Alert C The radiation wavelength lies outside the expected range for the supplied radiation type. Expected range 1.54175-1.54180 Wavelength given = 1.54056 PLAT_721 Alert C Bond Calc 0.91967, Rep 0.93000, Dev. 0.01 Ang. C14 -H14 1.555 1.555 PLAT_722 Alert C Angle Calc 117.59, Rep 119.00, Dev. 1.41 Deg. C4 -C7 -H7 1.555 1.555 1.555 PLAT_722 Alert C Angle Calc 119.56, Rep 118.00, Dev. 1.56 Deg. C8 -C7 -H7 1.555 1.555 1.555 PLAT_722 Alert C Angle Calc 119.11, Rep 118.00, Dev. 1.11 Deg. C9 -C8 -H8 1.555 1.555 1.555 General Notes
RADNT_01 Extra text has been found in the _diffrn_radiation_type field. Radiation given as CuK\a~1~ Radiation identified as Cu K\a RADNW_01 The radiation wavelength given implies that Cu Kalpha1 has been used. Please check that this is correct. Wavelength given = 1.54056
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
5 Alert Level C = Please check

Comment top

4-(4'-Dimethylaminostyril)pyridine N-oxide, (I), is an unusual substance. It has two potential coordinating groups, N–O and NMe2, which are conjugated with each other through an extensive π-system. The question of the first site of protonation has been discussed previously (Titski et al., 1996; Korzhenevskaya & Rybatschenko, 1999). This compound is the subject of much research devoted to the investigation of complexes formed with Lewis acids (Andreev et al., 2002), intramolecular charge transfer (Andreev et al., 1998), nucleophilic properties (Rybatschenko et al., 2001; Lobanova, 2001), and biological activity (Anisimov et al., 2000). Compound (I) has apoptogenic and erythroid differentiation induction activity towards K-562 cells (Volkova et al., 2001). According to our data, the molecule of (I) studied here is the trans isomer. The IR spectrum contains a band at 970 cm−1, which shows the presence of a trans H—CC—H group. The NMR spectrum contains two signals for vicinal olefin protons with J = 16 Hz, characteristic of a trans isomer (Silverstein et al., 1977).

Experimental top

Compound (I) was synthesized acording to the method of Titski & Turovskaya (1990). IR spectra were measured from KBr discs, using a Specord M-80 spectrometer. NMR spectra were measured with a Bruker 300 spectrometer (300 MHz), in CDCl3 solution. Electronic spectra were measured using a Specord UV–vis spectrometer, in 96% ethanol and in chloroform.

Refinement top

Two X-ray powder diffraction patterns were measured in transmission mode on a Ginuier–de Wolf diffractometer and in reflection mode on an X'Pert X-ray powder diffraction system equipped with a standard resolution goniometer PW 3050/60 and proportional point detector PW 3011/20. The powder was sprinkled on the sample holder using a fine sieve to avoid preferred orientation. The thickness of the sample was no more 0.1 mm. During the exposures the specimen was spun in its plane to improve particle statistics. The unit-cell dimensions were determined with the indexing program TREOR (Werner et al., 1985) with M20 = 14 and F30 = 31, using the first 30 peak positions. The structure was solved by the grid-search procedure (Chernyshev & Schenk, 1998) and refined with the use of bond restraints by the MRIA program (Zlokazov & Chernyshev, 1992). The strength of restraints was a function of interatomic separation and, for intramolecular bond lengths, corresponds to an r.m.s. deviation of 0.03 Å. An additional restraint was applied to the planarity of the C15N2O fragment. H atoms were placed in geometrically calculated positions and allowed to refine using riding model constraints, with a common isotropic displacement parameter Uiso fixed at 0.05 Å2. A single overall Uiso parameter for non-H atoms was refined. The diffraction profiles and the differences between the measured and calculated profiles are shown in Fig. 3.

Computing details top

Data collection: local program; data reduction: local program; program(s) used to solve structure: MRIA (Zlokazov & Chernyshev, 1992); program(s) used to refine structure: MRIA; software used to prepare material for publication: MRIA and PARST (Nardelli, 1983).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with the atomic numbering.
[Figure 2] Fig. 2. A packing diagram for (I).
[Figure 3] Fig. 3. The Rietveld plot for (I), showing the observed and difference profiles. The reflection positions are shown above the observed profile.
4-(4-dimethylaminophenylethenyl)pyridine N-oxide top
Crystal data top
C15H16N2OZ = 4
Mr = 240.2F(000) = 512
Monoclinic, P21/nDx = 1.266 Mg m3
a = 26.822 (4) ÅCu Kα1 radiation, λ = 1.54056 Å
b = 7.758 (2) ÅT = 293 K
c = 6.079 (3) ÅParticle morphology: no specific habit
β = 94.03 (1)°yellow
V = 1262 (1) Å3flat_sheet, 20 × 20 mm
Data collection top
Philips Analytical XPert PRO X-ray diffraction system
diffractometer
Data collection mode: reflection
Radiation source: PW3373/00, line-focus sealed tubeScan method: step
PW3110/65, four Ge(220) crystals monochromator2θmin = 6°, 2θmax = 60°, 2θstep = 0.01°
Specimen mounting: The powder was sprinkled on the sample holder through a fine sieve. The thickness of the layer was no more than 0.1 mm.
Refinement top
Refinement on Inet162 parameters
Least-squares matrix: full with fixed elements per cycle112 restraints
Rp = 0.191 constraint
Rwp = 0.29H-atom parameters constrained
Rexp = 0.19Weighting scheme based on measured s.u.'s w(i) = 1/Iobs(i) at each point i
χ2 = 2.250(Δ/σ)max = 0.01
5401 data pointsBackground function: Chebyshev polynomial up to the 5th order
Profile function: split-type pseudo-Voigt (Toraya, 1986)Preferred orientation correction: Spherical harmonics expansion (Ahtee et al., 1989) up to the 6th order.
Crystal data top
C15H16N2Oβ = 94.03 (1)°
Mr = 240.2V = 1262 (1) Å3
Monoclinic, P21/nZ = 4
a = 26.822 (4) ÅCu Kα1 radiation, λ = 1.54056 Å
b = 7.758 (2) ÅT = 293 K
c = 6.079 (3) Åflat_sheet, 20 × 20 mm
Data collection top
Philips Analytical XPert PRO X-ray diffraction system
diffractometer
Scan method: step
Specimen mounting: The powder was sprinkled on the sample holder through a fine sieve. The thickness of the layer was no more than 0.1 mm.2θmin = 6°, 2θmax = 60°, 2θstep = 0.01°
Data collection mode: reflection
Refinement top
Rp = 0.195401 data points
Rwp = 0.29162 parameters
Rexp = 0.19112 restraints
χ2 = 2.250H-atom parameters constrained
Special details top

Experimental. specimen was rotated in its plane

Geometry. All e.s.d.'s 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.0708 (16)0.180 (6)0.545 (9)0.075 (3)*
C20.115 (2)0.269 (7)0.574 (12)0.075 (3)*
C30.156 (2)0.254 (8)0.425 (12)0.075 (3)*
C40.155 (2)0.147 (8)0.240 (12)0.075 (3)*
C50.111 (2)0.056 (8)0.208 (12)0.075 (3)*
C60.0696 (18)0.074 (8)0.361 (14)0.075 (3)*
C70.198 (2)0.130 (8)0.084 (11)0.075 (3)*
C80.241 (3)0.214 (8)0.106 (11)0.075 (3)*
C90.284 (2)0.197 (8)0.050 (13)0.075 (3)*
C100.328 (2)0.288 (7)0.017 (11)0.075 (3)*
C110.3689 (19)0.273 (8)0.166 (12)0.075 (3)*
C120.367 (2)0.165 (8)0.353 (11)0.075 (3)*
C130.323 (2)0.074 (8)0.385 (11)0.075 (3)*
C140.2818 (19)0.090 (8)0.235 (11)0.075 (3)*
N150.4075 (16)0.148 (6)0.502 (9)0.075 (3)*
C160.404 (2)0.038 (9)0.689 (13)0.075 (3)*
C170.452 (2)0.242 (7)0.467 (13)0.075 (3)*
O180.0320 (14)0.194 (5)0.685 (7)0.075 (3)*
H20.1170.3400.6960.051*
H30.1850.3150.4490.051*
H50.1090.0160.0870.051*
H60.0410.0120.3380.051*
H70.1950.0580.0370.051*
H80.2430.2860.2270.051*
H100.3290.3600.1060.051*
H110.3980.3340.1430.051*
H130.3210.0030.5080.051*
H140.2530.0300.2570.051*
H16A0.4350.0400.7780.051*
H16B0.3970.0780.6400.051*
H16C0.3780.0770.7760.051*
H17A0.4770.2170.5850.051*
H17B0.4450.3630.4650.051*
H17C0.4640.2080.3290.051*
Geometric parameters (Å, º) top
N15—C171.43 (8)N1—O181.30 (6)
N15—C161.43 (9)C6—H60.93
N15—C121.37 (7)C5—H50.93
C12—C111.42 (9)C2—H20.93
C12—C131.41 (8)C3—H30.93
C11—C101.38 (8)C7—H70.93
C13—C141.38 (8)C8—H80.93
C14—C91.40 (9)C14—H140.93
C10—C91.40 (8)C13—H130.93
C9—C81.44 (9)C11—H110.93
C8—C71.34 (9)C10—H100.93
C7—C41.44 (8)C16—H16A0.96
C4—C31.40 (9)C16—H16B0.96
C3—C21.39 (8)C16—H16C0.96
C4—C51.40 (8)C17—H17A0.96
C5—C61.39 (9)C17—H17B0.96
C2—N11.39 (7)C17—H17C0.96
C6—N11.39 (9)
C6—N1—O18121 (5)C10—C9—C14120 (6)
C2—N1—O18121 (4)C9—C10—H10120
C2—N1—C6118 (5)C9—C10—C11120 (5)
N1—C2—H2119C11—C10—H10120
N1—C2—C3122 (5)C10—C11—H11120
C3—C2—H2119C10—C11—C12121 (6)
C2—C3—H3120C12—C11—H11120
C2—C3—C4120 (6)C11—C12—N15121 (6)
C4—C3—H3120C11—C12—C13119 (5)
C3—C4—C7121 (6)C13—C12—N15120 (5)
C3—C4—C5119 (6)C12—C13—H13120
C5—C4—C7120 (5)C12—C13—C14120 (5)
C4—C5—H5120C14—C13—H13120
C4—C5—C6120 (5)C9—C14—C13121 (6)
C6—C5—H5120C13—C14—H14120
N1—C6—C5122 (6)C9—C14—H14120
C5—C6—H6119C12—N15—C17119 (5)
N1—C6—H6119C12—N15—C16119 (5)
C4—C7—H7119C16—N15—C17121 (5)
C4—C7—C8123 (6)N15—C16—H16C110
C8—C7—H7118N15—C16—H16B110
C7—C8—H8118N15—C16—H16A110
C7—C8—C9123 (6)N15—C17—H17C109
C9—C8—H8118N15—C17—H17B109
C8—C9—C14120 (6)N15—C17—H17A109
C8—C9—C10120 (5)

Experimental details

Crystal data
Chemical formulaC15H16N2O
Mr240.2
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)26.822 (4), 7.758 (2), 6.079 (3)
β (°) 94.03 (1)
V3)1262 (1)
Z4
Radiation typeCu Kα1, λ = 1.54056 Å
Specimen shape, size (mm)Flat_sheet, 20 × 20
Data collection
DiffractometerPhilips Analytical XPert PRO X-ray diffraction system
diffractometer
Specimen mountingThe powder was sprinkled on the sample holder through a fine sieve. The thickness of the layer was no more than 0.1 mm.
Data collection modeReflection
Scan methodStep
2θ values (°)2θmin = 6 2θmax = 60 2θstep = 0.01
Refinement
R factors and goodness of fitRp = 0.19, Rwp = 0.29, Rexp = 0.19, χ2 = 2.250
No. of data points5401
No. of parameters162
No. of restraints112
H-atom treatmentH-atom parameters constrained

Computer programs: local program, MRIA (Zlokazov & Chernyshev, 1992), MRIA and PARST (Nardelli, 1983).

 

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