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The crystal structures of two (E)-stilbazolium salts, namely 1-(2-chloro­benzyl)-4-[(E)-2-(3-hydroxy­phenyl)­ethenyl]pyridinium chloride hemihydrate, C20H17ClNO+·Cl-·0.5H2O, (I), and 1-(2-bromo­benzyl)-4-[(E)-2-(3-hydroxy­phenyl)­ethen­yl]­pyridinium bromide hemihydrate, C20H17BrNO+·Br-·0.5H2O, (II), are isomorphous; the isostructurality index is 99.3%. In both salts, the aza­styryl fragments are almost planar, while the rings of the benzyl groups are almost perpendicular to the aza­styryl planes. The building blocks of the structures are twofold symmetric hydrogen-bonded systems of two cations, two halide anions and one water mol­ecule, which lies on a twofold axis. In the crystal structure, these blocks are connected by means of weaker inter­actions, viz. van der Waals, weak hydrogen bonding and stacking. This study illustrates the robustness of certain supramolecular motifs created by a spectrum of intermolecular interactions in generating these isomorphous crystal structures.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108009037/ln3095sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108009037/ln3095Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108009037/ln3095IIsup3.hkl
Contains datablock II

CCDC references: 690193; 690194

Comment top

The salts of the derivatives of (E)-stilbazolium have been found to be useful for nonlinear optics [for instance, trans-4'-(dimethylamino)-N-methyl-4-stilbazolium p-toluenesulfonate, DAST (Marder et al., 1989, 1994)] or for the preparation of polymers (e.g. Bloch & Wright, 1989). Due to an almost planar conformation, similar to (E)-stilbene, and the conjugated double-bond system, some stilbazolium derivatives exhibit interesting photochemical properties (e.g. Usami et al., 1990). The maximum in the UV absorption spectrum, shifted to long wavelength due to the conjugated double-bond system, can be used in the testing of chromatographic stationary phases (Prukała et al., 2008). N-alkyl- or N-benzyl-substituted (E)-stilbazole derivatives show a broad spectrum of antimicrobial activity (e.g. Wyrzykiewicz et al., 1990; Prukała & Kędzia, 1999) and some of them have already been patented (e.g. MacDonald et al., 2007; Klein et al., 2007).

We decided to undertake a detailed structural study of the family of N-benzyl-stilbazole derivatives. Here, we report the crystal structures of two compounds, 1-(2-chlorobenzyl)-4-[(E)-2-(3-hydroxyphenyl)ethenyl]pyridinium chloride hemihydrate, (I), and 1-(2-bromobenzyl)-4-[(E)-2-(3-hydroxyphenyl)ethenyl]pyridinium bromide hemihydrate, (II).

Compounds (I) and (II) are isomorphous; they crystallize in the same space group, and the unit-cell dimensions and packing modes are similar (Fig. 1a and b). In order to gain some insight into the degree of isomorphism, we have used the descriptors introduced by Kálmán et al. (1991). The unit-cell similarity index, Π, defined as the difference between unity and the ratio of the sums of the orthogonalized unit-cell parameters, is almost ideal, at 0.01. The isostructurality index, which shows how close the positions of the atoms in the unit cells are, is defined by the sum of the differences between the positions of analogous atoms. In the case of (I) and (II), the value of this index is also close to the ideal value at 99.3%. Kubicki & Szafrański (1998) proposed a modification of this latter parameter, which takes the point group symmetry into account and gives a more absolute measure of the degree of isostructurality; it should be 1 for ideally isomorphous compounds and 0 for randomly distributed atoms. The value of this modified index for (I) and (II) is 0.96. The structures of the two molecules are so similar (Figs. 2, 3) that even normal probability plots (International Tables for X-ray Crystallography, 1974; Abrahams & Keve, 1971) for bond lengths (without C—X bonds) and all bond angles show no differences of a systematic nature. The correlation factors R2 are 0.982 and 0.975 for the bond lengths and angles, respectively.

The conformation of each molecule can be described using the dihedral angles between the planar fragments, namely the three rings (chlorophenyl A, pyridine B and hydroxyphenyl C) and the C11—C14C15—C16 bridge (D). The dihedral angles within the whole azastyryl fragments are small, while those between rings B and C are as low as 2.75 (12)° in (I) and 2.66 (17)° in (II). The plane of the ethenyl bridge is significantly more twisted with respect to the ring planes (the angles are around 6°). It might be noted that these twists have the same sense, so the rings are almost coplanar. The perfectly planar benzyl groups are almost perpendicular to the azastyryl moieties; the dihedral angles between rings A and B are as high as 76.57 (6)° for (I) and 75.84 (9)° for (II). These are close to typical values: in the Cambridge Structural Database (Version 5.29 of November 2007; Allen, 2002) there are 778 similar fragments (both pyridyl- and phenyl-benzyl) and the values of the dihedral angles between the rings are in the range 53–90° with a mean value of 77.7 (3)°.

The building blocks of the structures are symmetrical hydrogen-bonded fragments built of two cations, two halide anions and a water molecule which occupies a special position on a twofold axis (Table 1, Fig. 4). All strong hydrogen-bond donors are involved in the creation of these structures, so the further construction of the crystal structures utilizes weaker interactions. The blocks are connected into a three-dimensional structure by means of relatively strong C—H···O and C—H···X hydrogen bonds (see Table 1 and Fig. 1). Additionally, an interesting network of weak interactions involving π-electron systems is created (Fig. 5). The distances between the centroids of rings B and C from molecules related by the centre of symmetry (1 - x,1 - y,1 - z) are 3.540 (2) Å in (I) and 3.676 (2) Å in (II). The planes of the rings are almost parallel (dihedral angles of ca 2.8°); taking the offset into account the distances between the planes are ca 3.38 Å in both cases. These centrosymmetric dimers are connected to neighbouring ones, related by another centre of symmetry, by means of weak but directional C—H···π interactions with the C14C15 double bond (Table 1).

Experimental top

The general procedure for the synthesis of (I) and (II) is as follows. (E)-Azastilbenol-2' (5 mmol) was dissolved in boiling nitromethane (50 ml). Upon dissolution, the corresponding benzyl halide (25 mmol) was added. The reaction mixture was refluxed for 5 h and the precipitated solid was filtered off. Then, half the volume of nitromethane was removed from the filtrate using a rotary evaporator. The residue was cooled for 24 h and the precipitated solid was filtered off, washed with CH3NO2 and dried. The desired products were obtained by combining both fractions of solids and recrystallizing them from methanol. For (I), m.p. 470–473 K; for (II), m.p. 498–501 K. Spectroscopic data are in the archived CIF.

Refinement top

The choice of the non-standard space group I2/a (instead of C2/c) was as a result of the large values of the β angle [131.44° for (I) and 130.70° for (II)] in the latter case. The positions of the hydroxyl H atom in (I) and the unique water H atom in (II) were refined with a restrained O—H distance of 0.84 (1) Å. The positions and Uiso(H) of all other H atoms in (I) were refined freely, while in (II) they were placed in idealized positions and refined using a riding model, with C—H = 0.93–0.97 Å [Please check added text]. All H atoms in (II) were assigned Uiso(H) = 1.2Ueq(C).

Computing details top

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Siemens, 1989); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The crystal packing of (a) (I) and (b) (II), viewed along the a direction.
[Figure 2] Fig. 2. The molecule of (I), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are drawn as dashed lines.
[Figure 3] Fig. 3. The molecule of (II), with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are drawn as dashed lines.
[Figure 4] Fig. 4. The building block of the crystal structures, shown for (I). Hydrogen bonds are drawn as dashed lines. [Symmetry codes: (i) -1/2 + x, 1/2 + y, 1/2 + z; (ii) 1/2 - x, y,2 - z.]
[Figure 5] Fig. 5. The molecules of (I), connected by weak interactions that involve π electrons (see text for details). The interactions and hydrogen bonds are drawn as dashed lines. [Symmetry codes: (i) x, y, z; (ii) 1 - x, 1 - y, 1 - z; (iii) 3/2 - x, 3/2 - y, 1/2 - z; (iv) -1/2 + x, -1/2 + y, 1/2 + z.]
(I) 1-(2-chlorobenzyl)-4-[(E)-2-(3-hydroxyphenyl)ethenyl]pyridinium chloride hemihydrate top
Crystal data top
C20H17ClNO+·Cl·0.5H2OF(000) = 1528
Mr = 367.25Dx = 1.366 Mg m3
Monoclinic, I2/aMo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2yaCell parameters from 4084 reflections
a = 15.6100 (12) Åθ = 3–24°
b = 13.2847 (10) ŵ = 0.37 mm1
c = 17.2233 (13) ÅT = 295 K
β = 91.358 (6)°Block, colourless
V = 3570.7 (5) Å30.3 × 0.2 × 0.2 mm
Z = 8
Data collection top
Kuma KM4 CCD area-detector
diffractometer
3288 independent reflections
Radiation source: fine-focus sealed tube2229 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
ω scansθmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)
h = 1818
Tmin = 0.903, Tmax = 0.928k = 1616
10549 measured reflectionsl = 2017
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.21 w = 1/[σ2(Fo2) + (0.05P)2]
where P = (Fo2 + 2Fc2)/3
3288 reflections(Δ/σ)max = 0.001
294 parametersΔρmax = 0.22 e Å3
1 restraintΔρmin = 0.27 e Å3
Crystal data top
C20H17ClNO+·Cl·0.5H2OV = 3570.7 (5) Å3
Mr = 367.25Z = 8
Monoclinic, I2/aMo Kα radiation
a = 15.6100 (12) ŵ = 0.37 mm1
b = 13.2847 (10) ÅT = 295 K
c = 17.2233 (13) Å0.3 × 0.2 × 0.2 mm
β = 91.358 (6)°
Data collection top
Kuma KM4 CCD area-detector
diffractometer
3288 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2007)
2229 reflections with I > 2σ(I)
Tmin = 0.903, Tmax = 0.928Rint = 0.017
10549 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0361 restraint
wR(F2) = 0.104H atoms treated by a mixture of independent and constrained refinement
S = 1.21Δρmax = 0.22 e Å3
3288 reflectionsΔρmin = 0.27 e Å3
294 parameters
Special details top

Experimental. Spectroscopic data: (I) IR (KBr, cm-1): 3030.0, 2990.5, 2940.4, 1620.8, 1575.1, 1510.5, 1460.6, 1265.7, 1160.5, 1055.2,990.0, 935.9, 870.1, 748.6. 1H NMR (DMSO-d6): δ = 9.81 (s, 1H, -OH), 9.06 (d, J = 6.8 Hz, 2H, o-H in –+NC5H4), 8.34 (d, J = 6.8 Hz, 2H, m-H in –+NC5H4), 8.03 (d, J = 16.2 Hz, 1H, –+NC5H4-CH), 7.69–7.22 (m, 7H), 7.21 (s, 1H, o-H in phenyl ring), 6.95 (d, J = 7.5 Hz, 1H, p-H in phenyl ring), 5.99 (s, 2H, -CH2-N+). 13C NMR (DMSO-d6): δ = 157.8, 153.5, 144.5, 141.7, 136.1, 132.9, 131.7, 131.1, 129.9, 129.7, 128.0, 123.9,122.9, 119.0, 117.8, 114.6, 60.0. m.p. 470–473 K.

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
xyzUiso*/Ueq
O1W0.75000.3423 (2)0.50000.0880 (8)
H1WA0.716 (2)0.300 (3)0.531 (2)0.160 (14)*
C10.78397 (12)0.62420 (14)0.10035 (10)0.0491 (5)
Cl10.71821 (4)0.72679 (4)0.11712 (4)0.0811 (2)
C20.86727 (13)0.64177 (17)0.07922 (11)0.0561 (5)
H20.8844 (12)0.7080 (16)0.0739 (11)0.055 (5)*
C30.92080 (15)0.56250 (18)0.06680 (12)0.0615 (6)
H30.9804 (13)0.5769 (15)0.0515 (11)0.061 (6)*
C40.89226 (15)0.46597 (19)0.07464 (13)0.0657 (6)
H40.9292 (13)0.4077 (16)0.0669 (12)0.070 (6)*
C50.80819 (14)0.44776 (16)0.09495 (12)0.0564 (5)
H50.7890 (13)0.3781 (16)0.1002 (11)0.069 (6)*
C60.75284 (12)0.52680 (14)0.10841 (10)0.0459 (5)
C70.66198 (14)0.50636 (18)0.13054 (12)0.0543 (5)
H7A0.6465 (12)0.4365 (16)0.1201 (11)0.061 (6)*
H7B0.6220 (13)0.5541 (16)0.1070 (11)0.059 (6)*
N80.64949 (9)0.51866 (12)0.21565 (8)0.0471 (4)
C90.59245 (13)0.58583 (16)0.24177 (13)0.0558 (5)
H90.5610 (14)0.6265 (16)0.2018 (13)0.072 (6)*
C100.57958 (14)0.59714 (16)0.31935 (12)0.0570 (5)
H100.5376 (12)0.6412 (15)0.3363 (11)0.057 (6)*
C110.62580 (12)0.54012 (14)0.37345 (11)0.0480 (5)
C120.68355 (13)0.47080 (17)0.34404 (12)0.0529 (5)
H120.7124 (12)0.4296 (14)0.3758 (11)0.045 (5)*
C130.69390 (13)0.46087 (16)0.26622 (12)0.0510 (5)
H130.7319 (13)0.4147 (17)0.2441 (11)0.068 (6)*
C140.61720 (13)0.55005 (16)0.45695 (12)0.0533 (5)
H140.6555 (13)0.5085 (15)0.4908 (12)0.067 (6)*
C150.55798 (13)0.60570 (15)0.49147 (11)0.0494 (5)
H150.5157 (12)0.6448 (15)0.4591 (11)0.062 (6)*
C160.54635 (11)0.61733 (13)0.57538 (11)0.0452 (5)
C170.48510 (13)0.68467 (14)0.60095 (11)0.0496 (5)
H170.4497 (12)0.7204 (14)0.5625 (11)0.052 (5)*
C180.47185 (12)0.69927 (14)0.67949 (12)0.0507 (5)
O180.41092 (11)0.76638 (12)0.70035 (10)0.0728 (5)
H180.4022 (15)0.7635 (17)0.7475 (6)0.073 (8)*
C190.52022 (13)0.64576 (16)0.73299 (12)0.0562 (5)
H190.5119 (11)0.6536 (14)0.7852 (12)0.053 (5)*
C200.58050 (14)0.57837 (19)0.70838 (13)0.0638 (6)
H200.6134 (15)0.5416 (17)0.7443 (13)0.078 (7)*
C210.59357 (13)0.56333 (18)0.63016 (12)0.0556 (5)
H210.6331 (12)0.5156 (15)0.6163 (10)0.056 (6)*
Cl20.38041 (4)0.75662 (5)0.87690 (4)0.0856 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1W0.107 (2)0.0766 (17)0.0819 (17)0.0000.0285 (15)0.000
C10.0563 (12)0.0455 (11)0.0456 (11)0.0052 (9)0.0027 (9)0.0003 (9)
Cl10.0802 (4)0.0513 (3)0.1126 (5)0.0128 (3)0.0217 (4)0.0001 (3)
C20.0639 (14)0.0511 (12)0.0535 (12)0.0068 (11)0.0075 (10)0.0036 (11)
C30.0552 (13)0.0774 (16)0.0522 (12)0.0004 (12)0.0107 (11)0.0031 (12)
C40.0687 (15)0.0697 (15)0.0595 (14)0.0204 (12)0.0179 (11)0.0048 (12)
C50.0707 (14)0.0472 (12)0.0517 (12)0.0032 (11)0.0102 (10)0.0006 (10)
C60.0514 (11)0.0491 (11)0.0372 (9)0.0027 (9)0.0018 (8)0.0025 (9)
C70.0546 (13)0.0592 (14)0.0491 (12)0.0075 (11)0.0012 (10)0.0037 (11)
N80.0448 (9)0.0486 (9)0.0483 (9)0.0056 (7)0.0059 (7)0.0008 (8)
C90.0569 (13)0.0585 (13)0.0520 (12)0.0051 (10)0.0032 (10)0.0012 (11)
C100.0602 (13)0.0542 (12)0.0570 (13)0.0092 (10)0.0071 (11)0.0023 (11)
C110.0481 (11)0.0465 (11)0.0494 (11)0.0091 (9)0.0039 (9)0.0015 (9)
C120.0477 (12)0.0561 (12)0.0551 (12)0.0014 (9)0.0035 (10)0.0126 (11)
C130.0465 (11)0.0498 (12)0.0572 (12)0.0001 (9)0.0116 (10)0.0069 (10)
C140.0533 (12)0.0557 (12)0.0513 (12)0.0061 (10)0.0064 (10)0.0017 (10)
C150.0531 (12)0.0468 (11)0.0482 (11)0.0104 (9)0.0011 (10)0.0031 (10)
C160.0476 (11)0.0404 (10)0.0477 (11)0.0108 (8)0.0002 (9)0.0009 (9)
C170.0565 (12)0.0416 (10)0.0506 (12)0.0058 (9)0.0036 (10)0.0065 (10)
C180.0517 (12)0.0430 (10)0.0575 (12)0.0055 (9)0.0025 (10)0.0034 (10)
O180.0873 (12)0.0669 (10)0.0647 (11)0.0217 (8)0.0107 (9)0.0025 (9)
C190.0592 (13)0.0678 (14)0.0418 (12)0.0035 (11)0.0042 (10)0.0027 (11)
C200.0550 (13)0.0836 (16)0.0525 (13)0.0070 (12)0.0041 (11)0.0055 (12)
C210.0489 (12)0.0643 (14)0.0537 (13)0.0047 (10)0.0051 (10)0.0011 (11)
Cl20.0931 (5)0.0774 (4)0.0883 (5)0.0237 (3)0.0430 (4)0.0245 (3)
Geometric parameters (Å, º) top
O1W—H1WA0.95 (3)C11—C121.392 (3)
C1—C21.378 (3)C11—C141.454 (3)
C1—C61.390 (2)C12—C131.360 (3)
C1—Cl11.7346 (19)C12—H120.888 (19)
C2—C31.364 (3)C13—H130.94 (2)
C2—H20.93 (2)C14—C151.334 (3)
C3—C41.365 (3)C14—H140.99 (2)
C3—H30.99 (2)C15—C161.469 (3)
C4—C51.387 (3)C15—H151.00 (2)
C4—H40.98 (2)C16—C211.384 (3)
C5—C61.383 (3)C16—C171.389 (3)
C5—H50.98 (2)C17—C181.387 (3)
C6—C71.502 (3)C17—H170.976 (19)
C7—N81.492 (2)C18—O181.358 (2)
C7—H7A0.97 (2)C18—C191.375 (3)
C7—H7B0.97 (2)O18—H180.827 (10)
N8—C131.342 (2)C19—C201.373 (3)
N8—C91.346 (2)C19—H190.918 (19)
C9—C101.364 (3)C20—C211.382 (3)
C9—H90.99 (2)C20—H200.93 (2)
C10—C111.389 (3)C21—H210.920 (19)
C10—H100.93 (2)
C2—C1—C6121.20 (18)C10—C11—C14123.74 (19)
C2—C1—Cl1118.47 (16)C12—C11—C14119.72 (19)
C6—C1—Cl1120.34 (15)C13—C12—C11121.0 (2)
C3—C2—C1119.7 (2)C13—C12—H12118.5 (12)
C3—C2—H2122.7 (12)C11—C12—H12120.4 (12)
C1—C2—H2117.6 (12)N8—C13—C12120.8 (2)
C2—C3—C4120.5 (2)N8—C13—H13115.6 (12)
C2—C3—H3118.4 (12)C12—C13—H13123.6 (12)
C4—C3—H3121.2 (12)C15—C14—C11124.9 (2)
C3—C4—C5120.1 (2)C15—C14—H14117.4 (12)
C3—C4—H4122.4 (12)C11—C14—H14117.5 (12)
C5—C4—H4117.5 (12)C14—C15—C16126.8 (2)
C6—C5—C4120.6 (2)C14—C15—H15119.7 (11)
C6—C5—H5120.6 (12)C16—C15—H15113.5 (11)
C4—C5—H5118.8 (12)C21—C16—C17118.51 (18)
C5—C6—C1117.95 (18)C21—C16—C15122.68 (18)
C5—C6—C7120.18 (18)C17—C16—C15118.80 (18)
C1—C6—C7121.86 (18)C18—C17—C16121.28 (19)
N8—C7—C6112.06 (16)C18—C17—H17120.0 (11)
N8—C7—H7A104.4 (11)C16—C17—H17118.7 (11)
C6—C7—H7A110.9 (11)O18—C18—C19122.59 (18)
N8—C7—H7B103.9 (12)O18—C18—C17118.13 (19)
C6—C7—H7B112.2 (12)C19—C18—C17119.28 (19)
H7A—C7—H7B113.0 (17)C18—O18—H18111.2 (17)
C13—N8—C9119.88 (17)C20—C19—C18119.96 (19)
C13—N8—C7119.83 (17)C20—C19—H19119.3 (12)
C9—N8—C7120.27 (17)C18—C19—H19120.7 (12)
N8—C9—C10121.0 (2)C19—C20—C21120.9 (2)
N8—C9—H9116.6 (12)C19—C20—H20120.5 (14)
C10—C9—H9122.4 (12)C21—C20—H20118.6 (14)
C9—C10—C11120.7 (2)C20—C21—C16120.1 (2)
C9—C10—H10119.8 (12)C20—C21—H21117.8 (12)
C11—C10—H10119.4 (12)C16—C21—H21122.0 (12)
C10—C11—C12116.54 (18)
C6—C1—C2—C30.8 (3)C10—C11—C12—C130.5 (3)
Cl1—C1—C2—C3179.02 (16)C14—C11—C12—C13179.03 (18)
C1—C2—C3—C40.4 (3)C9—N8—C13—C121.5 (3)
C2—C3—C4—C50.4 (3)C7—N8—C13—C12179.99 (17)
C3—C4—C5—C60.8 (3)C11—C12—C13—N80.9 (3)
C4—C5—C6—C10.5 (3)C10—C11—C14—C158.0 (3)
C4—C5—C6—C7179.87 (19)C12—C11—C14—C15172.49 (19)
C2—C1—C6—C50.3 (3)C11—C14—C15—C16179.44 (17)
Cl1—C1—C6—C5179.49 (14)C14—C15—C16—C215.3 (3)
C2—C1—C6—C7179.31 (18)C14—C15—C16—C17175.16 (19)
Cl1—C1—C6—C70.9 (3)C21—C16—C17—C181.0 (3)
C5—C6—C7—N8101.2 (2)C15—C16—C17—C18179.48 (17)
C1—C6—C7—N879.2 (2)C16—C17—C18—O18179.94 (17)
C6—C7—N8—C1360.6 (2)C16—C17—C18—C190.2 (3)
C6—C7—N8—C9121.0 (2)O18—C18—C19—C20179.5 (2)
C13—N8—C9—C100.8 (3)C17—C18—C19—C200.3 (3)
C7—N8—C9—C10179.23 (19)C18—C19—C20—C210.1 (3)
N8—C9—C10—C110.7 (3)C19—C20—C21—C160.8 (3)
C9—C10—C11—C121.2 (3)C17—C16—C21—C201.3 (3)
C9—C10—C11—C14178.26 (19)C15—C16—C21—C20179.22 (18)
(II) 1-(2-bromobenzyl)-4-[(E)-2-(3-hydroxyphenyl)ethenyl]pyridinium bromide hemihydrate top
Crystal data top
C20H17BrNO+·Br·0.5H2OF(000) = 1816
Mr = 456.17Dx = 1.653 Mg m3
Monoclinic, I2/aMo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2yaCell parameters from 6672 reflections
a = 15.6975 (8) Åθ = 3–25°
b = 13.5505 (7) ŵ = 4.43 mm1
c = 17.2562 (10) ÅT = 294 K
β = 92.879 (4)°Block, colourless
V = 3665.9 (3) Å30.4 × 0.2 × 0.2 mm
Z = 8
Data collection top
Kuma KM4 CCD area-detector
diffractometer
3406 independent reflections
Radiation source: fine-focus sealed tube2132 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ω scansθmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan
CrysAlis RED; Oxford Diffraction, 2007)
h = 1918
Tmin = 0.186, Tmax = 0.412k = 1616
16057 measured reflectionsl = 2020
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.035P)2]
where P = (Fo2 + 2Fc2)/3
3406 reflections(Δ/σ)max = 0.001
225 parametersΔρmax = 0.34 e Å3
1 restraintΔρmin = 0.49 e Å3
Crystal data top
C20H17BrNO+·Br·0.5H2OV = 3665.9 (3) Å3
Mr = 456.17Z = 8
Monoclinic, I2/aMo Kα radiation
a = 15.6975 (8) ŵ = 4.43 mm1
b = 13.5505 (7) ÅT = 294 K
c = 17.2562 (10) Å0.4 × 0.2 × 0.2 mm
β = 92.879 (4)°
Data collection top
Kuma KM4 CCD area-detector
diffractometer
3406 independent reflections
Absorption correction: multi-scan
CrysAlis RED; Oxford Diffraction, 2007)
2132 reflections with I > 2σ(I)
Tmin = 0.186, Tmax = 0.412Rint = 0.026
16057 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0281 restraint
wR(F2) = 0.074H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.34 e Å3
3406 reflectionsΔρmin = 0.49 e Å3
225 parameters
Special details top

Experimental. Spectroscopic data: (II) IR (KBr, cm-1): 3160.1, 2980.7, 2930.9, 1595.3, 1545.0, 1440.6, 1251.8, 1150.1, 990.1, 952.7,870.0, 745.8, 682.6, 511.9. 1H NMR (DMSO-d6): δ = 9.75 (s, 1H,-OH), 8.98 (d, J = 6.7 Hz, 2H, o-H in –+NC5H4),8.33 (d, J = 6.8 Hz, 2H, m-H in –+NC5H4), 8.01 (d, J = 16.2 Hz, 1H, –+NC5H4-CH), 7.72 (d, J = 7.8 Hz, 1H, m-H in BrC6H4CH2-), 7.53–7.21 (m, 5H), 7.35 (d, J = 16.2 Hz, 1H, HOC6H4-CH), 7.16 (s, 1H, o-H in phenyl ring), 6.90 (d, J = 7.6 Hz, 1H, p-H in phenyl ring), 5.91 (s, 2H, -CH2-N+). 13C NMR (DMSO-d6): δ = 157.6, 153.5, 144.6, 141.7, 136.2, 133.2, 131.2, 130.9, 129.9, 128.5, 124.0, 123.1,122.9, 119.2, 117.7, 114.5, 62.2. m.p. 498–501 K.

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 > 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
xyzUiso*/Ueq
O1W0.75000.3473 (3)0.50000.0862 (11)
H1WA0.716 (2)0.314 (2)0.527 (2)0.103*
C10.78943 (18)0.62299 (19)0.10153 (15)0.0398 (7)
Br10.72086 (2)0.73495 (2)0.11863 (2)0.06630 (14)
C20.87273 (19)0.6386 (2)0.08250 (16)0.0496 (8)
H20.89360.70250.07800.059*
C30.92471 (19)0.5589 (2)0.07024 (17)0.0537 (8)
H30.98090.56880.05740.064*
C40.8938 (2)0.4651 (2)0.07685 (17)0.0550 (9)
H40.92920.41140.06860.066*
C50.81087 (19)0.4497 (2)0.09559 (16)0.0479 (8)
H50.79050.38560.09980.058*
C60.75707 (17)0.52886 (19)0.10828 (15)0.0383 (7)
C70.66525 (17)0.5093 (2)0.12722 (15)0.0449 (7)
H7A0.62830.55530.09850.054*
H7B0.64950.44310.11070.054*
N80.65187 (14)0.51971 (15)0.21181 (13)0.0393 (6)
C90.59476 (19)0.5856 (2)0.23682 (18)0.0478 (8)
H90.56400.62450.20100.057*
C100.58173 (18)0.5957 (2)0.31365 (17)0.0480 (8)
H100.54210.64140.32960.058*
C110.62700 (17)0.53840 (19)0.36921 (17)0.0392 (7)
C120.68337 (18)0.4692 (2)0.34086 (17)0.0438 (7)
H120.71380.42800.37530.053*
C130.69427 (17)0.4614 (2)0.26331 (17)0.0453 (8)
H130.73200.41450.24570.054*
C140.61770 (18)0.5473 (2)0.45234 (17)0.0455 (7)
H140.65500.51110.48490.055*
C150.56028 (17)0.60282 (19)0.48545 (16)0.0425 (7)
H150.52310.63820.45220.051*
C160.54906 (17)0.61448 (18)0.56835 (16)0.0386 (7)
C170.48876 (18)0.68242 (19)0.59130 (16)0.0442 (7)
H170.45710.71820.55390.053*
C180.47529 (18)0.6973 (2)0.66915 (17)0.0449 (7)
O180.41565 (15)0.76524 (13)0.68744 (13)0.0649 (6)
H180.40670.76110.73370.078*
C190.52132 (19)0.6443 (2)0.72476 (17)0.0488 (8)
H190.51270.65460.77710.059*
C200.58073 (19)0.5755 (2)0.70249 (18)0.0545 (8)
H200.61160.53920.74010.065*
C210.59442 (17)0.5604 (2)0.62496 (18)0.0475 (8)
H210.63420.51380.61060.057*
Br20.37663 (3)0.75723 (2)0.86960 (2)0.06969 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1W0.106 (3)0.080 (3)0.075 (3)0.0000.030 (2)0.000
C10.0460 (18)0.0371 (15)0.0363 (17)0.0054 (13)0.0023 (14)0.0008 (13)
Br10.0643 (2)0.04165 (19)0.0946 (3)0.00760 (15)0.0197 (2)0.00045 (17)
C20.052 (2)0.0497 (18)0.047 (2)0.0071 (15)0.0077 (16)0.0035 (15)
C30.0426 (19)0.075 (2)0.045 (2)0.0048 (17)0.0106 (15)0.0051 (17)
C40.058 (2)0.055 (2)0.053 (2)0.0173 (17)0.0129 (17)0.0046 (16)
C50.058 (2)0.0416 (17)0.0453 (19)0.0048 (14)0.0123 (16)0.0036 (14)
C60.0411 (17)0.0444 (17)0.0294 (16)0.0004 (14)0.0028 (13)0.0002 (13)
C70.050 (2)0.0460 (17)0.0392 (18)0.0074 (14)0.0020 (14)0.0049 (14)
N80.0386 (14)0.0395 (13)0.0403 (15)0.0049 (11)0.0048 (12)0.0003 (11)
C90.0479 (19)0.0449 (17)0.050 (2)0.0073 (14)0.0023 (15)0.0065 (15)
C100.049 (2)0.0469 (17)0.049 (2)0.0059 (14)0.0090 (16)0.0049 (15)
C110.0368 (17)0.0389 (15)0.0422 (18)0.0082 (13)0.0052 (14)0.0007 (14)
C120.0426 (18)0.0461 (17)0.0427 (19)0.0013 (14)0.0013 (15)0.0072 (14)
C130.0409 (18)0.0413 (16)0.054 (2)0.0011 (13)0.0076 (16)0.0022 (15)
C140.0431 (18)0.0485 (17)0.0452 (19)0.0033 (14)0.0047 (15)0.0004 (15)
C150.0446 (18)0.0374 (15)0.0452 (19)0.0090 (13)0.0001 (14)0.0010 (14)
C160.0409 (18)0.0350 (15)0.0401 (18)0.0117 (13)0.0034 (14)0.0036 (13)
C170.0534 (19)0.0386 (16)0.0407 (19)0.0032 (14)0.0015 (15)0.0011 (13)
C180.0516 (19)0.0349 (15)0.048 (2)0.0037 (14)0.0036 (16)0.0003 (14)
O180.0840 (17)0.0552 (13)0.0565 (14)0.0243 (12)0.0146 (13)0.0015 (11)
C190.057 (2)0.0520 (19)0.0379 (19)0.0036 (15)0.0032 (16)0.0001 (15)
C200.054 (2)0.064 (2)0.045 (2)0.0059 (16)0.0072 (16)0.0063 (16)
C210.0403 (19)0.0485 (18)0.053 (2)0.0050 (14)0.0001 (16)0.0023 (15)
Br20.0758 (3)0.0649 (2)0.0709 (3)0.01741 (18)0.0295 (2)0.01868 (18)
Geometric parameters (Å, º) top
O1W—H1WA0.855 (10)C11—C121.395 (4)
C1—C61.380 (3)C11—C141.454 (4)
C1—C21.380 (4)C12—C131.362 (4)
C1—Br11.892 (3)C12—H120.9300
C2—C31.377 (4)C13—H130.9300
C2—H20.9300C14—C151.326 (3)
C3—C41.367 (4)C14—H140.9300
C3—H30.9300C15—C161.459 (4)
C4—C51.373 (4)C15—H150.9300
C4—H40.9300C16—C211.389 (4)
C5—C61.389 (4)C16—C171.392 (4)
C5—H50.9300C17—C181.385 (4)
C6—C71.517 (3)C17—H170.9300
C7—N81.492 (3)C18—O181.361 (3)
C7—H7A0.9700C18—C191.374 (4)
C7—H7B0.9700O18—H180.8200
N8—C131.341 (3)C19—C201.387 (4)
N8—C91.351 (3)C19—H190.9300
C9—C101.359 (4)C20—C211.381 (4)
C9—H90.9300C20—H200.9300
C10—C111.399 (4)C21—H210.9300
C10—H100.9300
C6—C1—C2121.3 (2)C12—C11—C14119.9 (3)
C6—C1—Br1120.9 (2)C10—C11—C14123.9 (3)
C2—C1—Br1117.9 (2)C13—C12—C11120.7 (3)
C3—C2—C1119.5 (3)C13—C12—H12119.7
C3—C2—H2120.3C11—C12—H12119.7
C1—C2—H2120.3N8—C13—C12121.5 (3)
C4—C3—C2120.1 (3)N8—C13—H13119.2
C4—C3—H3120.0C12—C13—H13119.2
C2—C3—H3120.0C15—C14—C11125.2 (3)
C3—C4—C5120.3 (3)C15—C14—H14117.4
C3—C4—H4119.8C11—C14—H14117.4
C5—C4—H4119.8C14—C15—C16127.0 (3)
C4—C5—C6120.7 (3)C14—C15—H15116.5
C4—C5—H5119.6C16—C15—H15116.5
C6—C5—H5119.6C21—C16—C17118.7 (3)
C1—C6—C5118.1 (2)C21—C16—C15123.3 (3)
C1—C6—C7122.5 (2)C17—C16—C15117.9 (3)
C5—C6—C7119.4 (2)C18—C17—C16120.8 (3)
N8—C7—C6112.1 (2)C18—C17—H17119.6
N8—C7—H7A109.2C16—C17—H17119.6
C6—C7—H7A109.2O18—C18—C19122.3 (3)
N8—C7—H7B109.2O18—C18—C17117.6 (3)
C6—C7—H7B109.2C19—C18—C17120.0 (3)
H7A—C7—H7B107.9C18—O18—H18109.5
C13—N8—C9119.5 (2)C18—C19—C20119.7 (3)
C13—N8—C7120.2 (2)C18—C19—H19120.2
C9—N8—C7120.2 (2)C20—C19—H19120.2
N8—C9—C10120.9 (3)C21—C20—C19120.5 (3)
N8—C9—H9119.6C21—C20—H20119.7
C10—C9—H9119.6C19—C20—H20119.7
C9—C10—C11121.1 (3)C20—C21—C16120.2 (3)
C9—C10—H10119.4C20—C21—H21119.9
C11—C10—H10119.4C16—C21—H21119.9
C12—C11—C10116.2 (3)
C6—C1—C2—C30.2 (4)C10—C11—C12—C131.8 (4)
Br1—C1—C2—C3179.5 (2)C14—C11—C12—C13178.5 (2)
C1—C2—C3—C40.0 (5)C9—N8—C13—C122.3 (4)
C2—C3—C4—C50.1 (5)C7—N8—C13—C12180.0 (2)
C3—C4—C5—C60.1 (5)C11—C12—C13—N80.3 (4)
C2—C1—C6—C50.2 (4)C12—C11—C14—C15172.8 (3)
Br1—C1—C6—C5179.5 (2)C10—C11—C14—C156.8 (4)
C2—C1—C6—C7178.5 (3)C11—C14—C15—C16179.5 (2)
Br1—C1—C6—C71.8 (4)C14—C15—C16—C215.7 (4)
C4—C5—C6—C10.0 (4)C14—C15—C16—C17175.3 (3)
C4—C5—C6—C7178.7 (3)C21—C16—C17—C181.3 (4)
C1—C6—C7—N880.0 (3)C15—C16—C17—C18179.7 (2)
C5—C6—C7—N8101.4 (3)C16—C17—C18—O18179.7 (2)
C6—C7—N8—C1360.9 (3)C16—C17—C18—C190.4 (4)
C6—C7—N8—C9121.4 (3)O18—C18—C19—C20179.4 (3)
C13—N8—C9—C102.1 (4)C17—C18—C19—C200.5 (4)
C7—N8—C9—C10179.8 (2)C18—C19—C20—C210.5 (4)
N8—C9—C10—C110.1 (4)C19—C20—C21—C160.4 (4)
C9—C10—C11—C122.0 (4)C17—C16—C21—C201.2 (4)
C9—C10—C11—C14178.4 (3)C15—C16—C21—C20179.8 (3)

Experimental details

(I)(II)
Crystal data
Chemical formulaC20H17ClNO+·Cl·0.5H2OC20H17BrNO+·Br·0.5H2O
Mr367.25456.17
Crystal system, space groupMonoclinic, I2/aMonoclinic, I2/a
Temperature (K)295294
a, b, c (Å)15.6100 (12), 13.2847 (10), 17.2233 (13)15.6975 (8), 13.5505 (7), 17.2562 (10)
β (°) 91.358 (6) 92.879 (4)
V3)3570.7 (5)3665.9 (3)
Z88
Radiation typeMo KαMo Kα
µ (mm1)0.374.43
Crystal size (mm)0.3 × 0.2 × 0.20.4 × 0.2 × 0.2
Data collection
DiffractometerKuma KM4 CCD area-detector
diffractometer
Kuma KM4 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(CrysAlis RED; Oxford Diffraction, 2007)
Multi-scan
CrysAlis RED; Oxford Diffraction, 2007)
Tmin, Tmax0.903, 0.9280.186, 0.412
No. of measured, independent and
observed [I > 2σ(I)] reflections
10549, 3288, 2229 16057, 3406, 2132
Rint0.0170.026
(sin θ/λ)max1)0.6060.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.104, 1.21 0.028, 0.074, 1.07
No. of reflections32883406
No. of parameters294225
No. of restraints11
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.22, 0.270.34, 0.49

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Siemens, 1989).

Geometry of hydrogen bonds for (I) and (II) (Å, °) top
D—H···AD—HH···AD···AD—H···A
Compound (I)
O18—H18···Cl20.83 (3)2.27 (3)3.092 (2)179 (2)
O1W—H1WA···Cl2i0.95 (3)2.28 (3)3.1844 (12)158 (3)
C7—H7A···Cl2ii0.97 (2)2.60 (2)3.557 (2)167 (2)
C12—H12···O1W0.89 (2)2.49 (2)3.327 (3)157 (1)
C14—H14···O1W0.99 (2)2.66 (2)3.520 (3)145 (1)
C15—H15···Cl2iii1.00 (2)2.83 (2)3.829 (2)173 (1)
C2—H2···Cg4iv0.93 (2)3.00 (2)3.905 (2)167 (1)
Compound (II)
O18—H18···Br20.822.423.234 (2)177
O1W—H1WA···Br2i0.86 (3)2.48 (3)3.310 (2)165 (3)
C7—H7A···Br2ii0.972.773.672 (3)155
C12—H12···O1W0.932.463.328 (3)156
C14—H14···O1W0.932.683.487 (4)146
C15—H15···Br2iii0.933.003.915 (3)168
C2—H2···Cg4iv0.933.144.032 (4)162
Symmetry codes: (i) 1-x, -1/2+y, 3/2-z; (ii) 1-x, 1-y, 1-z; (iii) x, 3/2-y, -1/2+z; (iv) 3/2-x, 3/2-y, 1/2-z. Cg4 denotes the mid-point of the C14C15 double bond.
 

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