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The title compound, C34H26N4·2CH2Cl2, lies about an inversion center. The solvent mol­ecules interact with the benzene mol­ecule both through C—H...N hydrogen bonding to span pyridine N atoms of adjacent vinyl groups, possibly stabilizing the rotational conformation observed, and through a π interaction between a dichloromethane Cl atom and a pyridyl ring C—C bond of a c-glide-related mol­ecule. The benzene mol­ecules form stacks along the a axis such that two of the four olefin groups are properly oriented for photoreactivity (2+2 cyclo­dimerization).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103001276/ga1001sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103001276/ga1001Isup2.hkl
Contains datablock I

CCDC reference: 208013

Comment top

Polyvinyl aromatic polymers have been researched extensively as potentially active materials in optoelectronic devices (Bao et al., 1998). Monomeric precursors incorporate vinyl groups that photopolymerize through [2 + 2] cycloaddition, ultimately breaking the conjugation between aromatized systems (Hasegawa et al., 1969). We are investigating pyridyl diolefins as halogen-bonding donors and as bridging ligands for metal complexation. Specifically, we are interested in the role that the acceptor molecules or metal centers in these complexes play in orientation of the olefins to control photoactivity. The title compound, (I), offers the possibility of crosslinking in two dimensions to give a layered polymer with sustainable cavities. However, when (I) crystallizes as the methylene chloride solvate reported here, only one pair of para-olefin groups is properly oriented for photoactivity.

The 1,2,4,5-tetrakis(2-vinylpyridyl)benzene molecule is situated about an inversion center at the mid-point of the cell (see Fig. 1). The molecule is approximately planar (r.m.s. = 0.127 Å) with a slightly bowed shape. The pyridyl rings in the 2 and 4 positions, which are associated with atoms N1 and N2A, are displaced to the same side of the central benzene plane by 0.367 (3) and 0.203 (3) Å, respectively, and have dihedral angles to the central ring of 9.3 (2)° and 4.5 (2)°.

The methylene chloride solvent molecules span the two adjacent pyridyl rings on either side of the benzene ring through C—H···N interactions. Compound (I) has the potential for a wide variety of rotational conformers (one alternative is shown in the scheme), and this solvent interaction may act to stabilize the conformation observed. One of the Cl atoms (Cl1) of each of the two solvent molecules extends, approximately normal, from the molecular plane into a hydrophobic cavity of the molecules above and below the solvent molecule in the stack. Weak C—H···Cl interactions are present between two of the C/H groups in the cavity and this Cl atom. The resulting one-dimensional stacks pack in herringbone fashion, with adjacent stacks related by glide-plane symmetry (Fig. 2). There are also close contacts between atom Cl2 of the solvent molecule and the C9—C10 bonding pair of the glide-related stack (at x, 1.5 − y, −0.5 + z), with Cl···C distances of 3.295 (4) and 3.399 (4) Å, respectively, and a Cl···Centroid(C9—C10) distance of 3.278 (4) Å. This Cl-π interaction is very similar to many others that have been observed (Irving, 1997; Irving & Irving, 1994). There is one weak intramolecular contact between the proton on C11 and N2 (H···N = 2.51 (3) Å).

As a result of the crystal packing, molecules stacked along the a axis have inversion-related olefins (associated with C4 and C5) in close contact (centroid-to-centroid distance of 3.993 (6) Å) and exactly parallel. This distance is somewhat longer than that observed in related compounds – 3.910 Å in 1,4-bis[2-(2-pyridyl)vinyl]benzene (Nakanishi et al., 1972), 3.939 Å in 2,5-distyrylpyrazine (Sasada et al., 1971), and 3.846 (7)–3.941 (6) Å in a mixed crystal of these two compounds (Nakanishi et al., 1979) – but like these compounds (Hasegawa et al., 1973), (I) should be suitable for photoactivity by solid-state polymerization.

We have also prepared a chloroform solvate of 1,2,4,5-tetrakis(2-vinylpyridyl)benzene, but attempts to structurally characterize it have been unsuccessful because of its rapid solvent loss. Continuing investigation of 1,2,4,5-tetrakis(2-vinylpyridyl)benzene will focus on its potential for photoactivity, its solvent-inclusion behavior and the role that the solvent might play in isolating other rotational conformations.

Experimental top

In a heavy-walled flask, 0.30 g (0.52 mmol) of 1,2,4,5-tetraiodobenzene, 0.67 ml (6.2 mmol) of 2-vinylpyridine, 0.0046 g (4 mol%) of palladium(II) acetate, 0.0063 g (4 mol%) of tri(ο-tolyl)phosphine, 0.21 g (2.6 mmol) of sodium acetate and 15 ml of dimethylformamide were sealed under nitrogen and heated to 403 K with stirring for 4 d. The reaction mixture was quenched with water, extracted with dichloromethane, dried with magnesium sulfate and filtered. Following column chromatography (silica gel, hexane/dichloromethane), the resultant mixture was dissolved in dichloromethane and the solvent was allowed to slowly evaporate in a refrigerator. Several diffraction quality crystals were removed from the solution.

Computing details top

Data collection: CrystalClear(Rigaku Corp., 2001); cell refinement: CrystalClear (Rigaku Corp., 2001); data reduction: CrystalClear (Rigaku Corp., 2001); program(s) used to solve structure: SHELXTL, (Sheldrick,2000); program(s) used to refine structure: SHELXTL (Sheldrick, 2000); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2000).

Figures top
[Figure 1] Fig. 1. The molecular structure of three molecules of (I). Displacement ellipsoids are shown with 50% probability and H atoms are of arbitrary radii. (Symmetry code: (A) 1 − x, 1 − y, 1 − z.)
[Figure 2] Fig. 2. Packing diagram for (I), viewed down the c axis. Cl atoms are shown as 50% probability ellipsoids, N atoms are shown as shaded circles and C atoms are shown as open circles.
1,2,4,5-tetrakis(2'-vinylpyridyl)benzene-dichloromethane (1:2) top
Crystal data top
C34H26N4·2CH2Cl2F(000) = 684
Mr = 660.44Dx = 1.339 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8789 reflections
a = 8.928 (2) Åθ = 2.8–26.4°
b = 18.596 (4) ŵ = 0.39 mm1
c = 10.015 (2) ÅT = 298 K
β = 99.822 (6)°Rod, yellow
V = 1638.4 (6) Å30.41 × 0.14 × 0.12 mm
Z = 2
Data collection top
Mercury AFC8S
diffractometer
3339 independent reflections
Radiation source: fine-focus sealed tube2172 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.086
ω scansθmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan
(REQABA; Jacobson, 1998)
h = 1011
Tmin = 0.676, Tmax = 1.000k = 2323
15828 measured reflectionsl = 1212
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)] = 0.065Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137All H-atom parameters refined
S = 0.99 w = 1/[σ2(Fo2) + (0.0125P)2 + 1.973P]
where P = (Fo2 + 2Fc2)/3
3339 reflections(Δ/σ)max < 0.001
259 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C34H26N4·2CH2Cl2V = 1638.4 (6) Å3
Mr = 660.44Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.928 (2) ŵ = 0.39 mm1
b = 18.596 (4) ÅT = 298 K
c = 10.015 (2) Å0.41 × 0.14 × 0.12 mm
β = 99.822 (6)°
Data collection top
Mercury AFC8S
diffractometer
3339 independent reflections
Absorption correction: multi-scan
(REQABA; Jacobson, 1998)
2172 reflections with I > 2σ(I)
Tmin = 0.676, Tmax = 1.000Rint = 0.086
15828 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0650 restraints
wR(F2) = 0.137All H-atom parameters refined
S = 0.99Δρmax = 0.18 e Å3
3339 reflectionsΔρmin = 0.28 e Å3
259 parameters
Special details top

Experimental. REQABA Empirical Absorption Correction, Version 1.1, R·A·Jacobson, Molecular Structure Corp. 1996–1998

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.0891 (3)0.63113 (15)0.4618 (3)0.0548 (7)
N20.2441 (4)0.67215 (17)0.0440 (3)0.0634 (8)
C10.4369 (3)0.54020 (16)0.3839 (3)0.0408 (7)
C20.3587 (3)0.53603 (16)0.4954 (3)0.0409 (7)
C30.4262 (4)0.49630 (17)0.6081 (3)0.0447 (7)
H10.367 (3)0.4935 (16)0.683 (3)0.052 (9)*
C40.2099 (4)0.57042 (18)0.4919 (3)0.0466 (7)
H20.165 (4)0.5930 (18)0.404 (4)0.066 (10)*
C50.1285 (4)0.57177 (19)0.5897 (4)0.0529 (8)
H30.168 (4)0.5526 (18)0.676 (4)0.067 (11)*
C60.0233 (3)0.60410 (17)0.5814 (3)0.0469 (7)
C70.0950 (4)0.6056 (2)0.6927 (4)0.0648 (10)
H40.047 (4)0.587 (2)0.775 (4)0.077 (13)*
C80.2377 (5)0.6352 (2)0.6832 (5)0.0739 (12)
H50.285 (5)0.635 (2)0.762 (5)0.105 (15)*
C90.3043 (5)0.6629 (2)0.5623 (5)0.0685 (11)
H60.406 (5)0.681 (2)0.544 (4)0.097 (14)*
C100.2282 (4)0.6597 (2)0.4557 (4)0.0634 (10)
H70.265 (4)0.6750 (18)0.367 (4)0.061 (11)*
C110.3776 (4)0.58315 (18)0.2636 (3)0.0455 (7)
H80.287 (4)0.6096 (18)0.269 (3)0.068 (11)*
C120.4348 (4)0.5911 (2)0.1521 (3)0.0566 (9)
H90.533 (5)0.569 (2)0.140 (4)0.087 (13)*
C130.3722 (4)0.63698 (19)0.0368 (3)0.0496 (8)
C140.4410 (5)0.6431 (3)0.0756 (4)0.0910 (16)
H100.525 (6)0.617 (3)0.075 (5)0.13 (2)*
C150.3791 (6)0.6869 (3)0.1812 (5)0.0929 (17)
H110.425 (6)0.693 (3)0.247 (6)0.14 (2)*
C160.2519 (5)0.7233 (2)0.1738 (4)0.0693 (11)
H120.208 (4)0.754 (2)0.251 (4)0.081 (12)*
C170.1882 (6)0.7145 (2)0.0602 (4)0.0780 (13)
H130.108 (5)0.735 (2)0.053 (4)0.083 (14)*
Cl10.18376 (12)0.52390 (6)0.04942 (11)0.0779 (3)
Cl20.14710 (16)0.67646 (6)0.10044 (15)0.1020 (5)
H150.023 (5)0.591 (2)0.104 (4)0.083 (13)*
H140.062 (5)0.585 (2)0.230 (5)0.102 (16)*
C180.0699 (5)0.5913 (2)0.1369 (5)0.0692 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0459 (16)0.0631 (18)0.0565 (17)0.0064 (14)0.0121 (13)0.0004 (14)
N20.078 (2)0.068 (2)0.0463 (16)0.0220 (17)0.0193 (15)0.0163 (14)
C10.0435 (16)0.0441 (16)0.0357 (15)0.0024 (13)0.0090 (12)0.0023 (13)
C20.0373 (15)0.0478 (17)0.0379 (16)0.0005 (13)0.0079 (13)0.0002 (13)
C30.0440 (16)0.0544 (18)0.0378 (16)0.0023 (14)0.0131 (14)0.0019 (14)
C40.0435 (17)0.0555 (19)0.0413 (17)0.0051 (15)0.0085 (14)0.0037 (15)
C50.0514 (19)0.061 (2)0.0478 (19)0.0098 (16)0.0136 (16)0.0106 (17)
C60.0438 (17)0.0470 (18)0.0523 (19)0.0003 (14)0.0149 (15)0.0004 (15)
C70.057 (2)0.082 (3)0.060 (2)0.014 (2)0.0250 (19)0.009 (2)
C80.068 (3)0.085 (3)0.078 (3)0.009 (2)0.038 (2)0.004 (2)
C90.051 (2)0.074 (3)0.085 (3)0.002 (2)0.024 (2)0.013 (2)
C100.053 (2)0.072 (3)0.064 (2)0.0056 (19)0.0060 (19)0.001 (2)
C110.0408 (16)0.0564 (19)0.0407 (17)0.0068 (15)0.0109 (14)0.0060 (14)
C120.0446 (18)0.082 (2)0.0447 (19)0.0163 (18)0.0121 (15)0.0153 (18)
C130.0469 (17)0.066 (2)0.0360 (16)0.0001 (16)0.0067 (14)0.0061 (15)
C140.064 (3)0.153 (5)0.061 (3)0.033 (3)0.026 (2)0.043 (3)
C150.077 (3)0.149 (5)0.058 (3)0.012 (3)0.023 (2)0.044 (3)
C160.089 (3)0.068 (2)0.049 (2)0.004 (2)0.008 (2)0.0189 (19)
C170.097 (3)0.081 (3)0.060 (3)0.037 (3)0.024 (2)0.017 (2)
Cl10.0684 (6)0.0810 (7)0.0859 (7)0.0008 (5)0.0178 (5)0.0120 (6)
Cl20.1131 (10)0.0724 (7)0.1217 (11)0.0125 (7)0.0236 (8)0.0075 (7)
C180.065 (3)0.075 (3)0.066 (3)0.006 (2)0.007 (2)0.002 (2)
Geometric parameters (Å, º) top
N1—C61.338 (4)C9—H60.96 (4)
N1—C101.342 (4)C10—H70.93 (3)
N2—C131.330 (4)C11—C121.313 (4)
N2—C171.335 (5)C11—H80.96 (4)
C1—C3i1.388 (4)C12—C131.468 (4)
C1—C21.417 (4)C12—H90.99 (4)
C1—C111.467 (4)C13—C141.376 (5)
C2—C31.397 (4)C14—C151.374 (6)
C2—C41.469 (4)C14—H100.90 (5)
C3—C1i1.388 (4)C15—C161.335 (6)
C3—H10.99 (3)C15—H110.84 (6)
C4—C51.316 (4)C16—C171.366 (6)
C4—H21.00 (3)C16—H120.98 (4)
C5—C61.472 (4)C17—H130.82 (4)
C5—H30.94 (3)Cl1—C181.752 (4)
C6—C71.378 (5)Cl2—C181.741 (4)
C7—C81.376 (5)Cl2—C9ii3.295 (4)
C7—H40.92 (4)Cl2—C10ii3.399 (4)
C8—C91.356 (6)C18—H150.94 (4)
C8—H50.96 (5)C18—H140.93 (5)
C9—C101.361 (5)
C6—N1—C10116.8 (3)C9—C10—H7126 (2)
C13—N2—C17117.3 (3)C12—C11—C1128.4 (3)
C3i—C1—C2118.4 (3)C12—C11—H8117 (2)
C3i—C1—C11120.3 (3)C1—C11—H8115 (2)
C2—C1—C11121.3 (3)C11—C12—C13125.7 (3)
C3—C2—C1117.6 (3)C11—C12—H9123 (2)
C3—C2—C4120.9 (3)C13—C12—H9111 (2)
C1—C2—C4121.5 (3)N2—C13—C14120.8 (3)
C1i—C3—C2124.0 (3)N2—C13—C12117.3 (3)
C1i—C3—H1120.5 (18)C14—C13—C12121.9 (3)
C2—C3—H1115.4 (18)C15—C14—C13120.1 (4)
C5—C4—C2127.0 (3)C15—C14—H10124 (4)
C5—C4—H2117 (2)C13—C14—H10116 (4)
C2—C4—H2116 (2)C16—C15—C14119.5 (4)
C4—C5—C6125.8 (3)C16—C15—H11121 (4)
C4—C5—H3121 (2)C14—C15—H11120 (4)
C6—C5—H3114 (2)C15—C16—C17117.7 (4)
N1—C6—C7121.5 (3)C15—C16—H12118 (2)
N1—C6—C5117.6 (3)C17—C16—H12124 (2)
C7—C6—C5120.9 (3)N2—C17—C16124.7 (4)
C8—C7—C6120.3 (4)N2—C17—H13114 (3)
C8—C7—H4120 (2)C16—C17—H13121 (3)
C6—C7—H4120 (2)Cl2—C18—Cl1111.8 (2)
C9—C8—C7118.3 (4)Cl2—C18—H15106 (3)
C9—C8—H5124 (3)Cl1—C18—H15107 (2)
C7—C8—H5118 (3)Cl2—C18—H14106 (3)
C8—C9—C10118.8 (4)Cl1—C18—H14111 (3)
C8—C9—H6124 (3)H15—C18—H14115 (4)
C10—C9—H6117 (3)C18—Cl2—C9ii174.1 (2)
N1—C10—C9124.3 (4)C18—Cl2—C10ii162.3 (2)
N1—C10—H7110 (2)
C3i—C1—C2—C31.2 (5)C7—C8—C9—C100.5 (6)
C11—C1—C2—C3177.4 (3)C6—N1—C10—C90.3 (6)
C3i—C1—C2—C4177.1 (3)C8—C9—C10—N10.5 (6)
C11—C1—C2—C44.2 (4)C3i—C1—C11—C122.9 (5)
C1—C2—C3—C1i1.3 (5)C2—C1—C11—C12178.5 (4)
C4—C2—C3—C1i177.1 (3)C1—C11—C12—C13177.8 (3)
C3—C2—C4—C53.5 (5)C17—N2—C13—C141.5 (6)
C1—C2—C4—C5178.2 (3)C17—N2—C13—C12179.3 (4)
C2—C4—C5—C6177.3 (3)C11—C12—C13—N21.9 (6)
C10—N1—C6—C70.1 (5)C11—C12—C13—C14178.9 (4)
C10—N1—C6—C5179.3 (3)N2—C13—C14—C151.1 (8)
C4—C5—C6—N14.0 (5)C12—C13—C14—C15179.7 (5)
C4—C5—C6—C7176.6 (4)C13—C14—C15—C160.0 (9)
N1—C6—C7—C80.1 (6)C14—C15—C16—C170.5 (8)
C5—C6—C7—C8179.2 (4)C13—N2—C17—C160.9 (7)
C6—C7—C8—C90.4 (7)C15—C16—C17—N20.1 (8)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+3/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C18—H14···N10.93 (5)2.52 (5)3.371 (6)152 (4)
C18—H15···N20.94 (4)2.64 (4)3.445 (6)144 (3)
C16—H12···N2ii0.98 (4)2.54 (4)3.420 (5)149 (3)
C5—H3···Cl1iii0.94 (3)3.08 (4)3.982 (4)161 (3)
C12—H9···Cl1iv0.99 (4)2.95 (4)3.926 (4)167 (3)
Symmetry codes: (ii) x, y+3/2, z1/2; (iii) x, y+1, z+1; (iv) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC34H26N4·2CH2Cl2
Mr660.44
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)8.928 (2), 18.596 (4), 10.015 (2)
β (°) 99.822 (6)
V3)1638.4 (6)
Z2
Radiation typeMo Kα
µ (mm1)0.39
Crystal size (mm)0.41 × 0.14 × 0.12
Data collection
DiffractometerMercury AFC8S
diffractometer
Absorption correctionMulti-scan
(REQABA; Jacobson, 1998)
Tmin, Tmax0.676, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
15828, 3339, 2172
Rint0.086
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.137, 0.99
No. of reflections3339
No. of parameters259
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.18, 0.28

Computer programs: CrystalClear(Rigaku Corp., 2001), CrystalClear (Rigaku Corp., 2001), SHELXTL, (Sheldrick,2000), SHELXTL (Sheldrick, 2000).

Selected geometric parameters (Å, º) top
N1—C61.338 (4)C6—C71.378 (5)
N1—C101.342 (4)C7—C81.376 (5)
C1—C3i1.388 (4)C8—C91.356 (6)
C1—C21.417 (4)C9—C101.361 (5)
C1—C111.467 (4)Cl1—C181.752 (4)
C2—C31.397 (4)Cl2—C181.741 (4)
C2—C41.469 (4)Cl2—C9ii3.295 (4)
C4—C51.316 (4)Cl2—C10ii3.399 (4)
C5—C61.472 (4)
C6—N1—C10116.8 (3)N1—C6—C5117.6 (3)
C13—N2—C17117.3 (3)C7—C6—C5120.9 (3)
C3i—C1—C2118.4 (3)N1—C10—C9124.3 (4)
C3i—C1—C11120.3 (3)C12—C11—C1128.4 (3)
C2—C1—C11121.3 (3)C11—C12—C13125.7 (3)
C3—C2—C1117.6 (3)N2—C13—C14120.8 (3)
C3—C2—C4120.9 (3)N2—C13—C12117.3 (3)
C1—C2—C4121.5 (3)N2—C17—C16124.7 (4)
C1i—C3—C2124.0 (3)Cl2—C18—Cl1111.8 (2)
C5—C4—C2127.0 (3)C18—Cl2—C9ii174.1 (2)
C4—C5—C6125.8 (3)C18—Cl2—C10ii162.3 (2)
N1—C6—C7121.5 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+3/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C18—H14···N10.93 (5)2.52 (5)3.371 (6)152 (4)
C18—H15···N20.94 (4)2.64 (4)3.445 (6)144 (3)
C16—H12···N2ii0.98 (4)2.54 (4)3.420 (5)149 (3)
C5—H3···Cl1iii0.94 (3)3.08 (4)3.982 (4)161 (3)
C12—H9···Cl1iv0.99 (4)2.95 (4)3.926 (4)167 (3)
Symmetry codes: (ii) x, y+3/2, z1/2; (iii) x, y+1, z+1; (iv) x+1, y, z.
 

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