Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108009037/ln3095sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108009037/ln3095Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108009037/ln3095IIsup3.hkl |
CCDC references: 690193; 690194
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.
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).
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).
C20H17ClNO+·Cl−·0.5H2O | F(000) = 1528 |
Mr = 367.25 | Dx = 1.366 Mg m−3 |
Monoclinic, I2/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -I 2ya | Cell parameters from 4084 reflections |
a = 15.6100 (12) Å | θ = 3–24° |
b = 13.2847 (10) Å | µ = 0.37 mm−1 |
c = 17.2233 (13) Å | T = 295 K |
β = 91.358 (6)° | Block, colourless |
V = 3570.7 (5) Å3 | 0.3 × 0.2 × 0.2 mm |
Z = 8 |
Kuma KM4 CCD area-detector diffractometer | 3288 independent reflections |
Radiation source: fine-focus sealed tube | 2229 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω scans | θmax = 25.5°, θmin = 2.4° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | h = −18→18 |
Tmin = 0.903, Tmax = 0.928 | k = −16→16 |
10549 measured reflections | l = −20→17 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.104 | H 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 parameters | Δρmax = 0.22 e Å−3 |
1 restraint | Δρmin = −0.27 e Å−3 |
C20H17ClNO+·Cl−·0.5H2O | V = 3570.7 (5) Å3 |
Mr = 367.25 | Z = 8 |
Monoclinic, I2/a | Mo Kα radiation |
a = 15.6100 (12) Å | µ = 0.37 mm−1 |
b = 13.2847 (10) Å | T = 295 K |
c = 17.2233 (13) Å | 0.3 × 0.2 × 0.2 mm |
β = 91.358 (6)° |
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 = 0.928 | Rint = 0.017 |
10549 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 1 restraint |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.21 | Δρmax = 0.22 e Å−3 |
3288 reflections | Δρmin = −0.27 e Å−3 |
294 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1W | 0.7500 | 0.3423 (2) | 0.5000 | 0.0880 (8) | |
H1WA | 0.716 (2) | 0.300 (3) | 0.531 (2) | 0.160 (14)* | |
C1 | 0.78397 (12) | 0.62420 (14) | 0.10035 (10) | 0.0491 (5) | |
Cl1 | 0.71821 (4) | 0.72679 (4) | 0.11712 (4) | 0.0811 (2) | |
C2 | 0.86727 (13) | 0.64177 (17) | 0.07922 (11) | 0.0561 (5) | |
H2 | 0.8844 (12) | 0.7080 (16) | 0.0739 (11) | 0.055 (5)* | |
C3 | 0.92080 (15) | 0.56250 (18) | 0.06680 (12) | 0.0615 (6) | |
H3 | 0.9804 (13) | 0.5769 (15) | 0.0515 (11) | 0.061 (6)* | |
C4 | 0.89226 (15) | 0.46597 (19) | 0.07464 (13) | 0.0657 (6) | |
H4 | 0.9292 (13) | 0.4077 (16) | 0.0669 (12) | 0.070 (6)* | |
C5 | 0.80819 (14) | 0.44776 (16) | 0.09495 (12) | 0.0564 (5) | |
H5 | 0.7890 (13) | 0.3781 (16) | 0.1002 (11) | 0.069 (6)* | |
C6 | 0.75284 (12) | 0.52680 (14) | 0.10841 (10) | 0.0459 (5) | |
C7 | 0.66198 (14) | 0.50636 (18) | 0.13054 (12) | 0.0543 (5) | |
H7A | 0.6465 (12) | 0.4365 (16) | 0.1201 (11) | 0.061 (6)* | |
H7B | 0.6220 (13) | 0.5541 (16) | 0.1070 (11) | 0.059 (6)* | |
N8 | 0.64949 (9) | 0.51866 (12) | 0.21565 (8) | 0.0471 (4) | |
C9 | 0.59245 (13) | 0.58583 (16) | 0.24177 (13) | 0.0558 (5) | |
H9 | 0.5610 (14) | 0.6265 (16) | 0.2018 (13) | 0.072 (6)* | |
C10 | 0.57958 (14) | 0.59714 (16) | 0.31935 (12) | 0.0570 (5) | |
H10 | 0.5376 (12) | 0.6412 (15) | 0.3363 (11) | 0.057 (6)* | |
C11 | 0.62580 (12) | 0.54012 (14) | 0.37345 (11) | 0.0480 (5) | |
C12 | 0.68355 (13) | 0.47080 (17) | 0.34404 (12) | 0.0529 (5) | |
H12 | 0.7124 (12) | 0.4296 (14) | 0.3758 (11) | 0.045 (5)* | |
C13 | 0.69390 (13) | 0.46087 (16) | 0.26622 (12) | 0.0510 (5) | |
H13 | 0.7319 (13) | 0.4147 (17) | 0.2441 (11) | 0.068 (6)* | |
C14 | 0.61720 (13) | 0.55005 (16) | 0.45695 (12) | 0.0533 (5) | |
H14 | 0.6555 (13) | 0.5085 (15) | 0.4908 (12) | 0.067 (6)* | |
C15 | 0.55798 (13) | 0.60570 (15) | 0.49147 (11) | 0.0494 (5) | |
H15 | 0.5157 (12) | 0.6448 (15) | 0.4591 (11) | 0.062 (6)* | |
C16 | 0.54635 (11) | 0.61733 (13) | 0.57538 (11) | 0.0452 (5) | |
C17 | 0.48510 (13) | 0.68467 (14) | 0.60095 (11) | 0.0496 (5) | |
H17 | 0.4497 (12) | 0.7204 (14) | 0.5625 (11) | 0.052 (5)* | |
C18 | 0.47185 (12) | 0.69927 (14) | 0.67949 (12) | 0.0507 (5) | |
O18 | 0.41092 (11) | 0.76638 (12) | 0.70035 (10) | 0.0728 (5) | |
H18 | 0.4022 (15) | 0.7635 (17) | 0.7475 (6) | 0.073 (8)* | |
C19 | 0.52022 (13) | 0.64576 (16) | 0.73299 (12) | 0.0562 (5) | |
H19 | 0.5119 (11) | 0.6536 (14) | 0.7852 (12) | 0.053 (5)* | |
C20 | 0.58050 (14) | 0.57837 (19) | 0.70838 (13) | 0.0638 (6) | |
H20 | 0.6134 (15) | 0.5416 (17) | 0.7443 (13) | 0.078 (7)* | |
C21 | 0.59357 (13) | 0.56333 (18) | 0.63016 (12) | 0.0556 (5) | |
H21 | 0.6331 (12) | 0.5156 (15) | 0.6163 (10) | 0.056 (6)* | |
Cl2 | 0.38041 (4) | 0.75662 (5) | 0.87690 (4) | 0.0856 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1W | 0.107 (2) | 0.0766 (17) | 0.0819 (17) | 0.000 | 0.0285 (15) | 0.000 |
C1 | 0.0563 (12) | 0.0455 (11) | 0.0456 (11) | 0.0052 (9) | 0.0027 (9) | −0.0003 (9) |
Cl1 | 0.0802 (4) | 0.0513 (3) | 0.1126 (5) | 0.0128 (3) | 0.0217 (4) | −0.0001 (3) |
C2 | 0.0639 (14) | 0.0511 (12) | 0.0535 (12) | −0.0068 (11) | 0.0075 (10) | 0.0036 (11) |
C3 | 0.0552 (13) | 0.0774 (16) | 0.0522 (12) | 0.0004 (12) | 0.0107 (11) | 0.0031 (12) |
C4 | 0.0687 (15) | 0.0697 (15) | 0.0595 (14) | 0.0204 (12) | 0.0179 (11) | 0.0048 (12) |
C5 | 0.0707 (14) | 0.0472 (12) | 0.0517 (12) | 0.0032 (11) | 0.0102 (10) | 0.0006 (10) |
C6 | 0.0514 (11) | 0.0491 (11) | 0.0372 (9) | −0.0027 (9) | 0.0018 (8) | −0.0025 (9) |
C7 | 0.0546 (13) | 0.0592 (14) | 0.0491 (12) | −0.0075 (11) | 0.0012 (10) | −0.0037 (11) |
N8 | 0.0448 (9) | 0.0486 (9) | 0.0483 (9) | −0.0056 (7) | 0.0059 (7) | 0.0008 (8) |
C9 | 0.0569 (13) | 0.0585 (13) | 0.0520 (12) | 0.0051 (10) | 0.0032 (10) | 0.0012 (11) |
C10 | 0.0602 (13) | 0.0542 (12) | 0.0570 (13) | 0.0092 (10) | 0.0071 (11) | −0.0023 (11) |
C11 | 0.0481 (11) | 0.0465 (11) | 0.0494 (11) | −0.0091 (9) | 0.0039 (9) | 0.0015 (9) |
C12 | 0.0477 (12) | 0.0561 (12) | 0.0551 (12) | −0.0014 (9) | 0.0035 (10) | 0.0126 (11) |
C13 | 0.0465 (11) | 0.0498 (12) | 0.0572 (12) | −0.0001 (9) | 0.0116 (10) | 0.0069 (10) |
C14 | 0.0533 (12) | 0.0557 (12) | 0.0513 (12) | −0.0061 (10) | 0.0064 (10) | 0.0017 (10) |
C15 | 0.0531 (12) | 0.0468 (11) | 0.0482 (11) | −0.0104 (9) | 0.0011 (10) | 0.0031 (10) |
C16 | 0.0476 (11) | 0.0404 (10) | 0.0477 (11) | −0.0108 (8) | 0.0002 (9) | 0.0009 (9) |
C17 | 0.0565 (12) | 0.0416 (10) | 0.0506 (12) | −0.0058 (9) | −0.0036 (10) | 0.0065 (10) |
C18 | 0.0517 (12) | 0.0430 (10) | 0.0575 (12) | −0.0055 (9) | 0.0025 (10) | −0.0034 (10) |
O18 | 0.0873 (12) | 0.0669 (10) | 0.0647 (11) | 0.0217 (8) | 0.0107 (9) | −0.0025 (9) |
C19 | 0.0592 (13) | 0.0678 (14) | 0.0418 (12) | −0.0035 (11) | 0.0042 (10) | −0.0027 (11) |
C20 | 0.0550 (13) | 0.0836 (16) | 0.0525 (13) | 0.0070 (12) | −0.0041 (11) | 0.0055 (12) |
C21 | 0.0489 (12) | 0.0643 (14) | 0.0537 (13) | 0.0047 (10) | 0.0051 (10) | 0.0011 (11) |
Cl2 | 0.0931 (5) | 0.0774 (4) | 0.0883 (5) | −0.0237 (3) | 0.0430 (4) | −0.0245 (3) |
O1W—H1WA | 0.95 (3) | C11—C12 | 1.392 (3) |
C1—C2 | 1.378 (3) | C11—C14 | 1.454 (3) |
C1—C6 | 1.390 (2) | C12—C13 | 1.360 (3) |
C1—Cl1 | 1.7346 (19) | C12—H12 | 0.888 (19) |
C2—C3 | 1.364 (3) | C13—H13 | 0.94 (2) |
C2—H2 | 0.93 (2) | C14—C15 | 1.334 (3) |
C3—C4 | 1.365 (3) | C14—H14 | 0.99 (2) |
C3—H3 | 0.99 (2) | C15—C16 | 1.469 (3) |
C4—C5 | 1.387 (3) | C15—H15 | 1.00 (2) |
C4—H4 | 0.98 (2) | C16—C21 | 1.384 (3) |
C5—C6 | 1.383 (3) | C16—C17 | 1.389 (3) |
C5—H5 | 0.98 (2) | C17—C18 | 1.387 (3) |
C6—C7 | 1.502 (3) | C17—H17 | 0.976 (19) |
C7—N8 | 1.492 (2) | C18—O18 | 1.358 (2) |
C7—H7A | 0.97 (2) | C18—C19 | 1.375 (3) |
C7—H7B | 0.97 (2) | O18—H18 | 0.827 (10) |
N8—C13 | 1.342 (2) | C19—C20 | 1.373 (3) |
N8—C9 | 1.346 (2) | C19—H19 | 0.918 (19) |
C9—C10 | 1.364 (3) | C20—C21 | 1.382 (3) |
C9—H9 | 0.99 (2) | C20—H20 | 0.93 (2) |
C10—C11 | 1.389 (3) | C21—H21 | 0.920 (19) |
C10—H10 | 0.93 (2) | ||
C2—C1—C6 | 121.20 (18) | C10—C11—C14 | 123.74 (19) |
C2—C1—Cl1 | 118.47 (16) | C12—C11—C14 | 119.72 (19) |
C6—C1—Cl1 | 120.34 (15) | C13—C12—C11 | 121.0 (2) |
C3—C2—C1 | 119.7 (2) | C13—C12—H12 | 118.5 (12) |
C3—C2—H2 | 122.7 (12) | C11—C12—H12 | 120.4 (12) |
C1—C2—H2 | 117.6 (12) | N8—C13—C12 | 120.8 (2) |
C2—C3—C4 | 120.5 (2) | N8—C13—H13 | 115.6 (12) |
C2—C3—H3 | 118.4 (12) | C12—C13—H13 | 123.6 (12) |
C4—C3—H3 | 121.2 (12) | C15—C14—C11 | 124.9 (2) |
C3—C4—C5 | 120.1 (2) | C15—C14—H14 | 117.4 (12) |
C3—C4—H4 | 122.4 (12) | C11—C14—H14 | 117.5 (12) |
C5—C4—H4 | 117.5 (12) | C14—C15—C16 | 126.8 (2) |
C6—C5—C4 | 120.6 (2) | C14—C15—H15 | 119.7 (11) |
C6—C5—H5 | 120.6 (12) | C16—C15—H15 | 113.5 (11) |
C4—C5—H5 | 118.8 (12) | C21—C16—C17 | 118.51 (18) |
C5—C6—C1 | 117.95 (18) | C21—C16—C15 | 122.68 (18) |
C5—C6—C7 | 120.18 (18) | C17—C16—C15 | 118.80 (18) |
C1—C6—C7 | 121.86 (18) | C18—C17—C16 | 121.28 (19) |
N8—C7—C6 | 112.06 (16) | C18—C17—H17 | 120.0 (11) |
N8—C7—H7A | 104.4 (11) | C16—C17—H17 | 118.7 (11) |
C6—C7—H7A | 110.9 (11) | O18—C18—C19 | 122.59 (18) |
N8—C7—H7B | 103.9 (12) | O18—C18—C17 | 118.13 (19) |
C6—C7—H7B | 112.2 (12) | C19—C18—C17 | 119.28 (19) |
H7A—C7—H7B | 113.0 (17) | C18—O18—H18 | 111.2 (17) |
C13—N8—C9 | 119.88 (17) | C20—C19—C18 | 119.96 (19) |
C13—N8—C7 | 119.83 (17) | C20—C19—H19 | 119.3 (12) |
C9—N8—C7 | 120.27 (17) | C18—C19—H19 | 120.7 (12) |
N8—C9—C10 | 121.0 (2) | C19—C20—C21 | 120.9 (2) |
N8—C9—H9 | 116.6 (12) | C19—C20—H20 | 120.5 (14) |
C10—C9—H9 | 122.4 (12) | C21—C20—H20 | 118.6 (14) |
C9—C10—C11 | 120.7 (2) | C20—C21—C16 | 120.1 (2) |
C9—C10—H10 | 119.8 (12) | C20—C21—H21 | 117.8 (12) |
C11—C10—H10 | 119.4 (12) | C16—C21—H21 | 122.0 (12) |
C10—C11—C12 | 116.54 (18) | ||
C6—C1—C2—C3 | −0.8 (3) | C10—C11—C12—C13 | 0.5 (3) |
Cl1—C1—C2—C3 | 179.02 (16) | C14—C11—C12—C13 | −179.03 (18) |
C1—C2—C3—C4 | 0.4 (3) | C9—N8—C13—C12 | −1.5 (3) |
C2—C3—C4—C5 | 0.4 (3) | C7—N8—C13—C12 | 179.99 (17) |
C3—C4—C5—C6 | −0.8 (3) | C11—C12—C13—N8 | 0.9 (3) |
C4—C5—C6—C1 | 0.5 (3) | C10—C11—C14—C15 | 8.0 (3) |
C4—C5—C6—C7 | −179.87 (19) | C12—C11—C14—C15 | −172.49 (19) |
C2—C1—C6—C5 | 0.3 (3) | C11—C14—C15—C16 | 179.44 (17) |
Cl1—C1—C6—C5 | −179.49 (14) | C14—C15—C16—C21 | −5.3 (3) |
C2—C1—C6—C7 | −179.31 (18) | C14—C15—C16—C17 | 175.16 (19) |
Cl1—C1—C6—C7 | 0.9 (3) | C21—C16—C17—C18 | 1.0 (3) |
C5—C6—C7—N8 | 101.2 (2) | C15—C16—C17—C18 | −179.48 (17) |
C1—C6—C7—N8 | −79.2 (2) | C16—C17—C18—O18 | 179.94 (17) |
C6—C7—N8—C13 | −60.6 (2) | C16—C17—C18—C19 | −0.2 (3) |
C6—C7—N8—C9 | 121.0 (2) | O18—C18—C19—C20 | 179.5 (2) |
C13—N8—C9—C10 | 0.8 (3) | C17—C18—C19—C20 | −0.3 (3) |
C7—N8—C9—C10 | 179.23 (19) | C18—C19—C20—C21 | 0.1 (3) |
N8—C9—C10—C11 | 0.7 (3) | C19—C20—C21—C16 | 0.8 (3) |
C9—C10—C11—C12 | −1.2 (3) | C17—C16—C21—C20 | −1.3 (3) |
C9—C10—C11—C14 | 178.26 (19) | C15—C16—C21—C20 | 179.22 (18) |
C20H17BrNO+·Br−·0.5H2O | F(000) = 1816 |
Mr = 456.17 | Dx = 1.653 Mg m−3 |
Monoclinic, I2/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -I 2ya | Cell parameters from 6672 reflections |
a = 15.6975 (8) Å | θ = 3–25° |
b = 13.5505 (7) Å | µ = 4.43 mm−1 |
c = 17.2562 (10) Å | T = 294 K |
β = 92.879 (4)° | Block, colourless |
V = 3665.9 (3) Å3 | 0.4 × 0.2 × 0.2 mm |
Z = 8 |
Kuma KM4 CCD area-detector diffractometer | 3406 independent reflections |
Radiation source: fine-focus sealed tube | 2132 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 25.5°, θmin = 2.6° |
Absorption correction: multi-scan CrysAlis RED; Oxford Diffraction, 2007) | h = −19→18 |
Tmin = 0.186, Tmax = 0.412 | k = −16→16 |
16057 measured reflections | l = −20→20 |
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)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.074 | H 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 parameters | Δρmax = 0.34 e Å−3 |
1 restraint | Δρmin = −0.49 e Å−3 |
C20H17BrNO+·Br−·0.5H2O | V = 3665.9 (3) Å3 |
Mr = 456.17 | Z = 8 |
Monoclinic, I2/a | Mo Kα radiation |
a = 15.6975 (8) Å | µ = 4.43 mm−1 |
b = 13.5505 (7) Å | T = 294 K |
c = 17.2562 (10) Å | 0.4 × 0.2 × 0.2 mm |
β = 92.879 (4)° |
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 = 0.412 | Rint = 0.026 |
16057 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 1 restraint |
wR(F2) = 0.074 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.34 e Å−3 |
3406 reflections | Δρmin = −0.49 e Å−3 |
225 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1W | 0.7500 | 0.3473 (3) | 0.5000 | 0.0862 (11) | |
H1WA | 0.716 (2) | 0.314 (2) | 0.527 (2) | 0.103* | |
C1 | 0.78943 (18) | 0.62299 (19) | 0.10153 (15) | 0.0398 (7) | |
Br1 | 0.72086 (2) | 0.73495 (2) | 0.11863 (2) | 0.06630 (14) | |
C2 | 0.87273 (19) | 0.6386 (2) | 0.08250 (16) | 0.0496 (8) | |
H2 | 0.8936 | 0.7025 | 0.0780 | 0.059* | |
C3 | 0.92471 (19) | 0.5589 (2) | 0.07024 (17) | 0.0537 (8) | |
H3 | 0.9809 | 0.5688 | 0.0574 | 0.064* | |
C4 | 0.8938 (2) | 0.4651 (2) | 0.07685 (17) | 0.0550 (9) | |
H4 | 0.9292 | 0.4114 | 0.0686 | 0.066* | |
C5 | 0.81087 (19) | 0.4497 (2) | 0.09559 (16) | 0.0479 (8) | |
H5 | 0.7905 | 0.3856 | 0.0998 | 0.058* | |
C6 | 0.75707 (17) | 0.52886 (19) | 0.10828 (15) | 0.0383 (7) | |
C7 | 0.66525 (17) | 0.5093 (2) | 0.12722 (15) | 0.0449 (7) | |
H7A | 0.6283 | 0.5553 | 0.0985 | 0.054* | |
H7B | 0.6495 | 0.4431 | 0.1107 | 0.054* | |
N8 | 0.65187 (14) | 0.51971 (15) | 0.21181 (13) | 0.0393 (6) | |
C9 | 0.59476 (19) | 0.5856 (2) | 0.23682 (18) | 0.0478 (8) | |
H9 | 0.5640 | 0.6245 | 0.2010 | 0.057* | |
C10 | 0.58173 (18) | 0.5957 (2) | 0.31365 (17) | 0.0480 (8) | |
H10 | 0.5421 | 0.6414 | 0.3296 | 0.058* | |
C11 | 0.62700 (17) | 0.53840 (19) | 0.36921 (17) | 0.0392 (7) | |
C12 | 0.68337 (18) | 0.4692 (2) | 0.34086 (17) | 0.0438 (7) | |
H12 | 0.7138 | 0.4280 | 0.3753 | 0.053* | |
C13 | 0.69427 (17) | 0.4614 (2) | 0.26331 (17) | 0.0453 (8) | |
H13 | 0.7320 | 0.4145 | 0.2457 | 0.054* | |
C14 | 0.61770 (18) | 0.5473 (2) | 0.45234 (17) | 0.0455 (7) | |
H14 | 0.6550 | 0.5111 | 0.4849 | 0.055* | |
C15 | 0.56028 (17) | 0.60282 (19) | 0.48545 (16) | 0.0425 (7) | |
H15 | 0.5231 | 0.6382 | 0.4522 | 0.051* | |
C16 | 0.54906 (17) | 0.61448 (18) | 0.56835 (16) | 0.0386 (7) | |
C17 | 0.48876 (18) | 0.68242 (19) | 0.59130 (16) | 0.0442 (7) | |
H17 | 0.4571 | 0.7182 | 0.5539 | 0.053* | |
C18 | 0.47529 (18) | 0.6973 (2) | 0.66915 (17) | 0.0449 (7) | |
O18 | 0.41565 (15) | 0.76524 (13) | 0.68744 (13) | 0.0649 (6) | |
H18 | 0.4067 | 0.7611 | 0.7337 | 0.078* | |
C19 | 0.52132 (19) | 0.6443 (2) | 0.72476 (17) | 0.0488 (8) | |
H19 | 0.5127 | 0.6546 | 0.7771 | 0.059* | |
C20 | 0.58073 (19) | 0.5755 (2) | 0.70249 (18) | 0.0545 (8) | |
H20 | 0.6116 | 0.5392 | 0.7401 | 0.065* | |
C21 | 0.59442 (17) | 0.5604 (2) | 0.62496 (18) | 0.0475 (8) | |
H21 | 0.6342 | 0.5138 | 0.6106 | 0.057* | |
Br2 | 0.37663 (3) | 0.75723 (2) | 0.86960 (2) | 0.06969 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1W | 0.106 (3) | 0.080 (3) | 0.075 (3) | 0.000 | 0.030 (2) | 0.000 |
C1 | 0.0460 (18) | 0.0371 (15) | 0.0363 (17) | 0.0054 (13) | 0.0023 (14) | 0.0008 (13) |
Br1 | 0.0643 (2) | 0.04165 (19) | 0.0946 (3) | 0.00760 (15) | 0.0197 (2) | −0.00045 (17) |
C2 | 0.052 (2) | 0.0497 (18) | 0.047 (2) | −0.0071 (15) | 0.0077 (16) | 0.0035 (15) |
C3 | 0.0426 (19) | 0.075 (2) | 0.045 (2) | 0.0048 (17) | 0.0106 (15) | 0.0051 (17) |
C4 | 0.058 (2) | 0.055 (2) | 0.053 (2) | 0.0173 (17) | 0.0129 (17) | 0.0046 (16) |
C5 | 0.058 (2) | 0.0416 (17) | 0.0453 (19) | 0.0048 (14) | 0.0123 (16) | 0.0036 (14) |
C6 | 0.0411 (17) | 0.0444 (17) | 0.0294 (16) | 0.0004 (14) | 0.0028 (13) | 0.0002 (13) |
C7 | 0.050 (2) | 0.0460 (17) | 0.0392 (18) | −0.0074 (14) | 0.0020 (14) | −0.0049 (14) |
N8 | 0.0386 (14) | 0.0395 (13) | 0.0403 (15) | −0.0049 (11) | 0.0048 (12) | 0.0003 (11) |
C9 | 0.0479 (19) | 0.0449 (17) | 0.050 (2) | 0.0073 (14) | 0.0023 (15) | 0.0065 (15) |
C10 | 0.049 (2) | 0.0469 (17) | 0.049 (2) | 0.0059 (14) | 0.0090 (16) | −0.0049 (15) |
C11 | 0.0368 (17) | 0.0389 (15) | 0.0422 (18) | −0.0082 (13) | 0.0052 (14) | −0.0007 (14) |
C12 | 0.0426 (18) | 0.0461 (17) | 0.0427 (19) | −0.0013 (14) | 0.0013 (15) | 0.0072 (14) |
C13 | 0.0409 (18) | 0.0413 (16) | 0.054 (2) | 0.0011 (13) | 0.0076 (16) | 0.0022 (15) |
C14 | 0.0431 (18) | 0.0485 (17) | 0.0452 (19) | −0.0033 (14) | 0.0047 (15) | −0.0004 (15) |
C15 | 0.0446 (18) | 0.0374 (15) | 0.0452 (19) | −0.0090 (13) | −0.0001 (14) | 0.0010 (14) |
C16 | 0.0409 (18) | 0.0350 (15) | 0.0401 (18) | −0.0117 (13) | 0.0034 (14) | −0.0036 (13) |
C17 | 0.0534 (19) | 0.0386 (16) | 0.0407 (19) | −0.0032 (14) | 0.0015 (15) | 0.0011 (13) |
C18 | 0.0516 (19) | 0.0349 (15) | 0.048 (2) | −0.0037 (14) | 0.0036 (16) | 0.0003 (14) |
O18 | 0.0840 (17) | 0.0552 (13) | 0.0565 (14) | 0.0243 (12) | 0.0146 (13) | 0.0015 (11) |
C19 | 0.057 (2) | 0.0520 (19) | 0.0379 (19) | −0.0036 (15) | 0.0032 (16) | −0.0001 (15) |
C20 | 0.054 (2) | 0.064 (2) | 0.045 (2) | 0.0059 (16) | −0.0072 (16) | 0.0063 (16) |
C21 | 0.0403 (19) | 0.0485 (18) | 0.053 (2) | 0.0050 (14) | −0.0001 (16) | −0.0023 (15) |
Br2 | 0.0758 (3) | 0.0649 (2) | 0.0709 (3) | −0.01741 (18) | 0.0295 (2) | −0.01868 (18) |
O1W—H1WA | 0.855 (10) | C11—C12 | 1.395 (4) |
C1—C6 | 1.380 (3) | C11—C14 | 1.454 (4) |
C1—C2 | 1.380 (4) | C12—C13 | 1.362 (4) |
C1—Br1 | 1.892 (3) | C12—H12 | 0.9300 |
C2—C3 | 1.377 (4) | C13—H13 | 0.9300 |
C2—H2 | 0.9300 | C14—C15 | 1.326 (3) |
C3—C4 | 1.367 (4) | C14—H14 | 0.9300 |
C3—H3 | 0.9300 | C15—C16 | 1.459 (4) |
C4—C5 | 1.373 (4) | C15—H15 | 0.9300 |
C4—H4 | 0.9300 | C16—C21 | 1.389 (4) |
C5—C6 | 1.389 (4) | C16—C17 | 1.392 (4) |
C5—H5 | 0.9300 | C17—C18 | 1.385 (4) |
C6—C7 | 1.517 (3) | C17—H17 | 0.9300 |
C7—N8 | 1.492 (3) | C18—O18 | 1.361 (3) |
C7—H7A | 0.9700 | C18—C19 | 1.374 (4) |
C7—H7B | 0.9700 | O18—H18 | 0.8200 |
N8—C13 | 1.341 (3) | C19—C20 | 1.387 (4) |
N8—C9 | 1.351 (3) | C19—H19 | 0.9300 |
C9—C10 | 1.359 (4) | C20—C21 | 1.381 (4) |
C9—H9 | 0.9300 | C20—H20 | 0.9300 |
C10—C11 | 1.399 (4) | C21—H21 | 0.9300 |
C10—H10 | 0.9300 | ||
C6—C1—C2 | 121.3 (2) | C12—C11—C14 | 119.9 (3) |
C6—C1—Br1 | 120.9 (2) | C10—C11—C14 | 123.9 (3) |
C2—C1—Br1 | 117.9 (2) | C13—C12—C11 | 120.7 (3) |
C3—C2—C1 | 119.5 (3) | C13—C12—H12 | 119.7 |
C3—C2—H2 | 120.3 | C11—C12—H12 | 119.7 |
C1—C2—H2 | 120.3 | N8—C13—C12 | 121.5 (3) |
C4—C3—C2 | 120.1 (3) | N8—C13—H13 | 119.2 |
C4—C3—H3 | 120.0 | C12—C13—H13 | 119.2 |
C2—C3—H3 | 120.0 | C15—C14—C11 | 125.2 (3) |
C3—C4—C5 | 120.3 (3) | C15—C14—H14 | 117.4 |
C3—C4—H4 | 119.8 | C11—C14—H14 | 117.4 |
C5—C4—H4 | 119.8 | C14—C15—C16 | 127.0 (3) |
C4—C5—C6 | 120.7 (3) | C14—C15—H15 | 116.5 |
C4—C5—H5 | 119.6 | C16—C15—H15 | 116.5 |
C6—C5—H5 | 119.6 | C21—C16—C17 | 118.7 (3) |
C1—C6—C5 | 118.1 (2) | C21—C16—C15 | 123.3 (3) |
C1—C6—C7 | 122.5 (2) | C17—C16—C15 | 117.9 (3) |
C5—C6—C7 | 119.4 (2) | C18—C17—C16 | 120.8 (3) |
N8—C7—C6 | 112.1 (2) | C18—C17—H17 | 119.6 |
N8—C7—H7A | 109.2 | C16—C17—H17 | 119.6 |
C6—C7—H7A | 109.2 | O18—C18—C19 | 122.3 (3) |
N8—C7—H7B | 109.2 | O18—C18—C17 | 117.6 (3) |
C6—C7—H7B | 109.2 | C19—C18—C17 | 120.0 (3) |
H7A—C7—H7B | 107.9 | C18—O18—H18 | 109.5 |
C13—N8—C9 | 119.5 (2) | C18—C19—C20 | 119.7 (3) |
C13—N8—C7 | 120.2 (2) | C18—C19—H19 | 120.2 |
C9—N8—C7 | 120.2 (2) | C20—C19—H19 | 120.2 |
N8—C9—C10 | 120.9 (3) | C21—C20—C19 | 120.5 (3) |
N8—C9—H9 | 119.6 | C21—C20—H20 | 119.7 |
C10—C9—H9 | 119.6 | C19—C20—H20 | 119.7 |
C9—C10—C11 | 121.1 (3) | C20—C21—C16 | 120.2 (3) |
C9—C10—H10 | 119.4 | C20—C21—H21 | 119.9 |
C11—C10—H10 | 119.4 | C16—C21—H21 | 119.9 |
C12—C11—C10 | 116.2 (3) | ||
C6—C1—C2—C3 | −0.2 (4) | C10—C11—C12—C13 | 1.8 (4) |
Br1—C1—C2—C3 | 179.5 (2) | C14—C11—C12—C13 | −178.5 (2) |
C1—C2—C3—C4 | 0.0 (5) | C9—N8—C13—C12 | −2.3 (4) |
C2—C3—C4—C5 | 0.1 (5) | C7—N8—C13—C12 | 180.0 (2) |
C3—C4—C5—C6 | −0.1 (5) | C11—C12—C13—N8 | 0.3 (4) |
C2—C1—C6—C5 | 0.2 (4) | C12—C11—C14—C15 | −172.8 (3) |
Br1—C1—C6—C5 | −179.5 (2) | C10—C11—C14—C15 | 6.8 (4) |
C2—C1—C6—C7 | −178.5 (3) | C11—C14—C15—C16 | −179.5 (2) |
Br1—C1—C6—C7 | 1.8 (4) | C14—C15—C16—C21 | −5.7 (4) |
C4—C5—C6—C1 | 0.0 (4) | C14—C15—C16—C17 | 175.3 (3) |
C4—C5—C6—C7 | 178.7 (3) | C21—C16—C17—C18 | 1.3 (4) |
C1—C6—C7—N8 | −80.0 (3) | C15—C16—C17—C18 | −179.7 (2) |
C5—C6—C7—N8 | 101.4 (3) | C16—C17—C18—O18 | 179.7 (2) |
C6—C7—N8—C13 | −60.9 (3) | C16—C17—C18—C19 | −0.4 (4) |
C6—C7—N8—C9 | 121.4 (3) | O18—C18—C19—C20 | 179.4 (3) |
C13—N8—C9—C10 | 2.1 (4) | C17—C18—C19—C20 | −0.5 (4) |
C7—N8—C9—C10 | 179.8 (2) | C18—C19—C20—C21 | 0.5 (4) |
N8—C9—C10—C11 | 0.1 (4) | C19—C20—C21—C16 | 0.4 (4) |
C9—C10—C11—C12 | −2.0 (4) | C17—C16—C21—C20 | −1.2 (4) |
C9—C10—C11—C14 | 178.4 (3) | C15—C16—C21—C20 | 179.8 (3) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C20H17ClNO+·Cl−·0.5H2O | C20H17BrNO+·Br−·0.5H2O |
Mr | 367.25 | 456.17 |
Crystal system, space group | Monoclinic, I2/a | Monoclinic, I2/a |
Temperature (K) | 295 | 294 |
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) |
V (Å3) | 3570.7 (5) | 3665.9 (3) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.37 | 4.43 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 | 0.4 × 0.2 × 0.2 |
Data collection | ||
Diffractometer | Kuma KM4 CCD area-detector diffractometer | Kuma KM4 CCD area-detector diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2007) | Multi-scan CrysAlis RED; Oxford Diffraction, 2007) |
Tmin, Tmax | 0.903, 0.928 | 0.186, 0.412 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10549, 3288, 2229 | 16057, 3406, 2132 |
Rint | 0.017 | 0.026 |
(sin θ/λ)max (Å−1) | 0.606 | 0.606 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.104, 1.21 | 0.028, 0.074, 1.07 |
No. of reflections | 3288 | 3406 |
No. of parameters | 294 | 225 |
No. of restraints | 1 | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.27 | 0.34, −0.49 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Siemens, 1989).
D—H···A | D—H | H···A | D···A | D—H···A |
Compound (I) | ||||
O18—H18···Cl2 | 0.83 (3) | 2.27 (3) | 3.092 (2) | 179 (2) |
O1W—H1WA···Cl2i | 0.95 (3) | 2.28 (3) | 3.1844 (12) | 158 (3) |
C7—H7A···Cl2ii | 0.97 (2) | 2.60 (2) | 3.557 (2) | 167 (2) |
C12—H12···O1W | 0.89 (2) | 2.49 (2) | 3.327 (3) | 157 (1) |
C14—H14···O1W | 0.99 (2) | 2.66 (2) | 3.520 (3) | 145 (1) |
C15—H15···Cl2iii | 1.00 (2) | 2.83 (2) | 3.829 (2) | 173 (1) |
C2—H2···Cg4iv | 0.93 (2) | 3.00 (2) | 3.905 (2) | 167 (1) |
Compound (II) | ||||
O18—H18···Br2 | 0.82 | 2.42 | 3.234 (2) | 177 |
O1W—H1WA···Br2i | 0.86 (3) | 2.48 (3) | 3.310 (2) | 165 (3) |
C7—H7A···Br2ii | 0.97 | 2.77 | 3.672 (3) | 155 |
C12—H12···O1W | 0.93 | 2.46 | 3.328 (3) | 156 |
C14—H14···O1W | 0.93 | 2.68 | 3.487 (4) | 146 |
C15—H15···Br2iii | 0.93 | 3.00 | 3.915 (3) | 168 |
C2—H2···Cg4iv | 0.93 | 3.14 | 4.032 (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 C14═C15 double bond. |
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—C14═C15—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 C14═C15 double bond (Table 1).