Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004731/cv6013sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004731/cv6013Isup2.hkl |
CCDC reference: 162827
1,4-Bis[(4-pyridyl)ethynyl]benzene was prepared according to the literature (Lin et al., 1995). Chloranilic acid was commercially available and purified by a usual method. A diffusion method for a solution of 1,4-bis[(4-pyridyl)ethynyl]benzene (0.02 mmol) and chloranilic acid (0.02 mmol) in acetonitrile (5 ml) using an H-tube gave crystals of (I) suitable for X-ray analysis.
We have recently shown that the simple combination of chloranilic acid and dipyridyl-type ligands can create a variety of supramolecular architectures involving infinite one-dimensional molecular tape structures (Zaman et al., 1999, 2000). In the course of our crystal engineering studies on chloranilic acid, we have obtained the title compound, (I), a 1:1 co-crystal of chloranilic acid and 1,4-bis[(4-pyridyl)ethynyl]benzene. A long rigid and conjugated bridging ligand has received much current interest for the construction of self-assembling macrocyclic architectures (Lehn, 1995; Fujita, 1999) and the development of molecular wires (Tour, 1996). However, we have found only two examples (Lin et al., 1995, 1998) of the structures containing a 1,4-bis[(4-pyridyl)ethynyl]benzene unit in the Cambridge Structural Database (Allen & Kennard, 1993). We report here the structure of (I) with the hydrogen-bonded molecular tapes.
The molecular structure of (I) is shown in Fig. 1, and both molecules are located on the inversion center. A one-dimensional molecular tape is observed in the structure of (I), as shown in Fig. 2. The molecular tape is nearly flat. The angles between the molecular planes of the chloranilate and the pyridinium ring, and of the pyridinium ring and the benzene ring are 7.3 (2) and 11.8 (4)°, respectively. The molecular tapes are connected via R12(5) couplings with two intermolecular N—H···O hydrogen bonds (Table 1), where both H atoms of chloranilic acid have transfered to the pyridine rings. In previous work (Zaman et al., 2000), we have shown that the flat molecular tapes form segregated stacks of each molecule. However, the overlaps between the chloranilate–pyridinium ring–benzene ring–pyridinium ring–chloranilate are observed in the stacks of the molecular tapes of (I). A short C—Cl···π interaction [Cl1···(C7≡C8) 3.440 (7), Cl1···C7 3.503 (4), Cl1···C8 3.480 (4) Å; Cl1···C7≡C8 79.1 (3) and Cl1···C8≡C7 81.3 (3)°] exists between the stacks of the molecular tapes (Reddy et al., 1996; Prasanna & Row, 2000). It is 1.7% shorter than the sum of the van der Waals radii of Cl and Csp2 (Pauling, 1960).
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
C20H14N22+·C6Cl2O42− | Z = 1 |
Mr = 489.29 | F(000) = 250 |
Triclinic, P1 | Dx = 1.514 Mg m−3 |
a = 7.6279 (9) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 8.4019 (10) Å | Cell parameters from 23 reflections |
c = 8.6291 (4) Å | θ = 5.9–43.0° |
α = 97.171 (6)° | µ = 3.05 mm−1 |
β = 99.673 (6)° | T = 296 K |
γ = 95.728 (10)° | Needle, dark red |
V = 536.76 (9) Å3 | 0.70 × 0.10 × 0.10 mm |
Enraf-Nonius CAD-4 diffractometer | 1213 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.041 |
Graphite monochromator | θmax = 74.3°, θmin = 5.3° |
ω–2θ scans | h = −9→9 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→10 |
Tmin = 0.224, Tmax = 0.750 | l = 0→10 |
2340 measured reflections | 3 standard reflections every 120 reflections |
2187 independent reflections | intensity decay: 2.5% |
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)] = 0.053 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.161 | All H-atom parameters refined |
S = 0.99 | |
2187 reflections | (Δ/σ)max < 0.001 |
182 parameters | Δρmax = 0.29 e Å−3 |
0 restraints | Δρmin = −0.37 e Å−3 |
C20H14N22+·C6Cl2O42− | γ = 95.728 (10)° |
Mr = 489.29 | V = 536.76 (9) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.6279 (9) Å | Cu Kα radiation |
b = 8.4019 (10) Å | µ = 3.05 mm−1 |
c = 8.6291 (4) Å | T = 296 K |
α = 97.171 (6)° | 0.70 × 0.10 × 0.10 mm |
β = 99.673 (6)° |
Enraf-Nonius CAD-4 diffractometer | 1213 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.041 |
Tmin = 0.224, Tmax = 0.750 | 3 standard reflections every 120 reflections |
2340 measured reflections | intensity decay: 2.5% |
2187 independent reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.161 | All H-atom parameters refined |
S = 0.99 | Δρmax = 0.29 e Å−3 |
2187 reflections | Δρmin = −0.37 e Å−3 |
182 parameters |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 6.1356 (0.0040) x + 4.1372 (0.0088) y - 3.1134 (0.0136) z = 2.5275 (0.0119) * -0.0539 (0.0017) Cl1 * 0.0295 (0.0014) O1 * -0.0465 (0.0021) O2 * 0.0378 (0.0024) C1 * 0.0260 (0.0032) C2 * 0.0071 (0.0026) C3 Rms deviation of fitted atoms = 0.0367 5.5220 (0.0102) x + 4.9362 (0.0131) y - 3.4671 (0.0127) z = 1.6612 (0.0039) Angle to previous plane (with approximate e.s.d.) = 7.25 (0.22) * 0.0008 (0.0030) N1 * -0.0014 (0.0028) C9 * 0.0023 (0.0032) C10 * -0.0020 (0.0032) C11 * 0.0001 (0.0032) C12 * 0.0003 (0.0031) C13 Rms deviation of fitted atoms = 0.0014 4.3368 (0.0174) x + 6.0836 (0.0213) y - 3.8662 (0.0550) z = 1.3554 (0.0571) Angle to previous plane (with approximate e.s.d.) = 11.78 (0.39) * 0.0000 (0.0001) C4 * 0.0000 (0.0000) C5 * 0.0000 (0.0000) C6 Rms deviation of fitted atoms = 0.0000 |
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 | ||
Cl1 | 0.20224 (16) | 0.69132 (13) | 0.52271 (10) | 0.0753 (4) | |
O1 | 0.0000 (3) | 0.7946 (3) | 0.2345 (2) | 0.0620 (8) | |
O2 | −0.1897 (4) | 1.0442 (3) | 0.2169 (2) | 0.0649 (8) | |
N1 | 0.2126 (5) | 0.1379 (4) | 0.0556 (3) | 0.0629 (10) | |
C1 | 0.0961 (5) | 0.8620 (4) | 0.5109 (3) | 0.0493 (9) | |
C2 | 0.0021 (5) | 0.8856 (4) | 0.3607 (3) | 0.0461 (8) | |
C3 | −0.1024 (5) | 1.0290 (4) | 0.3516 (3) | 0.0467 (9) | |
C4 | 0.3538 (6) | 0.5481 (5) | 0.9087 (4) | 0.0641 (12) | |
C5 | 0.4490 (5) | 0.4367 (4) | 0.8403 (3) | 0.0499 (9) | |
C6 | 0.5969 (6) | 0.3893 (5) | 0.9317 (4) | 0.0630 (12) | |
C7 | 0.3978 (5) | 0.3700 (5) | 0.6751 (3) | 0.0561 (10) | |
C8 | 0.3564 (5) | 0.3164 (5) | 0.5379 (4) | 0.0590 (11) | |
C9 | 0.3064 (5) | 0.2549 (5) | 0.3723 (3) | 0.0532 (10) | |
C10 | 0.1842 (6) | 0.3236 (6) | 0.2743 (4) | 0.0639 (12) | |
C11 | 0.1395 (7) | 0.2608 (6) | 0.1149 (4) | 0.0676 (13) | |
C12 | 0.3313 (7) | 0.0690 (5) | 0.1468 (4) | 0.0691 (13) | |
C13 | 0.3819 (6) | 0.1250 (5) | 0.3070 (4) | 0.0653 (12) | |
H1 | 0.181 (8) | 0.088 (8) | −0.065 (8) | 0.14 (2)* | |
H4 | 0.244 (6) | 0.583 (6) | 0.857 (6) | 0.093 (15)* | |
H6 | 0.670 (6) | 0.309 (6) | 0.896 (5) | 0.080 (14)* | |
H10 | 0.128 (5) | 0.407 (5) | 0.307 (4) | 0.053 (11)* | |
H11 | 0.065 (5) | 0.303 (5) | 0.064 (5) | 0.059 (13)* | |
H12 | 0.391 (6) | −0.025 (6) | 0.107 (5) | 0.082 (14)* | |
H13 | 0.469 (6) | 0.061 (5) | 0.369 (5) | 0.076 (13)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1005 (9) | 0.0774 (7) | 0.0370 (5) | 0.0335 (6) | −0.0130 (4) | −0.0172 (4) |
O1 | 0.0873 (19) | 0.0747 (17) | 0.0156 (9) | 0.0165 (15) | −0.0001 (10) | −0.0181 (10) |
O2 | 0.094 (2) | 0.0751 (17) | 0.0159 (10) | 0.0212 (15) | −0.0110 (11) | −0.0119 (10) |
N1 | 0.085 (2) | 0.078 (2) | 0.0144 (12) | −0.0085 (18) | 0.0026 (14) | −0.0115 (13) |
C1 | 0.064 (2) | 0.061 (2) | 0.0161 (13) | 0.0089 (17) | −0.0020 (13) | −0.0097 (13) |
C2 | 0.059 (2) | 0.056 (2) | 0.0148 (12) | 0.0004 (17) | −0.0007 (12) | −0.0116 (12) |
C3 | 0.061 (2) | 0.058 (2) | 0.0141 (12) | 0.0002 (17) | −0.0005 (12) | −0.0078 (12) |
C4 | 0.077 (3) | 0.091 (3) | 0.0180 (14) | 0.024 (2) | −0.0059 (16) | −0.0054 (16) |
C5 | 0.070 (2) | 0.058 (2) | 0.0132 (12) | −0.0025 (17) | −0.0017 (13) | −0.0050 (12) |
C6 | 0.090 (3) | 0.072 (3) | 0.0210 (15) | 0.020 (2) | −0.0022 (17) | −0.0105 (15) |
C7 | 0.074 (3) | 0.070 (2) | 0.0157 (13) | −0.0043 (19) | 0.0026 (14) | −0.0089 (14) |
C8 | 0.077 (3) | 0.074 (3) | 0.0174 (14) | −0.004 (2) | 0.0020 (15) | −0.0089 (15) |
C9 | 0.071 (3) | 0.065 (2) | 0.0140 (13) | −0.0136 (18) | 0.0036 (14) | −0.0094 (13) |
C10 | 0.080 (3) | 0.079 (3) | 0.0237 (16) | 0.004 (2) | 0.0015 (17) | −0.0155 (17) |
C11 | 0.081 (3) | 0.089 (3) | 0.0201 (15) | 0.002 (3) | −0.0083 (17) | −0.0069 (18) |
C12 | 0.103 (4) | 0.069 (3) | 0.0260 (17) | 0.006 (3) | 0.0052 (19) | −0.0156 (16) |
C13 | 0.099 (3) | 0.064 (2) | 0.0229 (16) | 0.005 (2) | −0.0027 (18) | −0.0075 (15) |
Cl1—C1 | 1.721 (4) | C5—C7 | 1.438 (3) |
O1—C2 | 1.246 (3) | C6—C4ii | 1.386 (4) |
O2—C3 | 1.266 (3) | C6—H6 | 0.97 (4) |
N1—C11 | 1.311 (6) | C7—C8 | 1.190 (4) |
N1—C12 | 1.324 (5) | C8—C9 | 1.431 (4) |
N1—H1 | 1.05 (7) | C9—C10 | 1.371 (5) |
C1—C3i | 1.397 (4) | C9—C13 | 1.386 (6) |
C1—C2 | 1.419 (4) | C10—C11 | 1.382 (4) |
C2—C3 | 1.513 (5) | C10—H10 | 0.90 (4) |
C3—C1i | 1.397 (4) | C11—H11 | 0.80 (4) |
C4—C5 | 1.376 (5) | C12—C13 | 1.379 (4) |
C4—C6ii | 1.386 (4) | C12—H12 | 1.01 (5) |
C4—H4 | 0.97 (5) | C13—H13 | 1.02 (4) |
C5—C6 | 1.387 (5) | ||
C11—N1—C12 | 121.0 (3) | C4ii—C6—H6 | 114 (3) |
C11—N1—H1 | 123 (3) | C5—C6—H6 | 126 (3) |
C12—N1—H1 | 116 (3) | C8—C7—C5 | 179.2 (4) |
C3i—C1—C2 | 122.1 (3) | C7—C8—C9 | 179.0 (4) |
C3i—C1—Cl1 | 119.4 (2) | C10—C9—C13 | 118.4 (3) |
C2—C1—Cl1 | 118.4 (2) | C10—C9—C8 | 121.0 (3) |
O1—C2—C1 | 123.8 (3) | C13—C9—C8 | 120.6 (3) |
O1—C2—C3 | 117.5 (3) | C9—C10—C11 | 119.3 (4) |
C1—C2—C3 | 118.6 (2) | C9—C10—H10 | 124 (2) |
O2—C3—C1i | 123.6 (3) | C11—C10—H10 | 117 (2) |
O2—C3—C2 | 117.3 (3) | N1—C11—C10 | 121.3 (4) |
C1i—C3—C2 | 119.2 (3) | N1—C11—H11 | 124 (3) |
C5—C4—C6ii | 120.4 (4) | C10—C11—H11 | 115 (3) |
C5—C4—H4 | 126 (3) | N1—C12—C13 | 120.9 (4) |
C6ii—C4—H4 | 113 (3) | N1—C12—H12 | 124 (2) |
C4—C5—C6 | 119.5 (3) | C13—C12—H12 | 115 (3) |
C4—C5—C7 | 120.8 (3) | C12—C13—C9 | 119.2 (4) |
C6—C5—C7 | 119.7 (3) | C12—C13—H13 | 116 (2) |
C4ii—C6—C5 | 120.0 (4) | C9—C13—H13 | 125 (2) |
C3i—C1—C2—O1 | 176.8 (4) | C4—C5—C6—C4ii | 1.1 (7) |
Cl1—C1—C2—O1 | −4.2 (5) | C7—C5—C6—C4ii | −179.4 (4) |
C3i—C1—C2—C3 | −3.2 (6) | C13—C9—C10—C11 | 0.5 (6) |
Cl1—C1—C2—C3 | 175.7 (3) | C8—C9—C10—C11 | 179.9 (4) |
O1—C2—C3—O2 | 2.2 (5) | C12—N1—C11—C10 | 0.4 (7) |
C1—C2—C3—O2 | −177.8 (3) | C9—C10—C11—N1 | −0.5 (7) |
O1—C2—C3—C1i | −176.9 (3) | C11—N1—C12—C13 | −0.2 (7) |
C1—C2—C3—C1i | 3.1 (6) | N1—C12—C13—C9 | 0.1 (7) |
C6ii—C4—C5—C6 | −1.1 (7) | C10—C9—C13—C12 | −0.3 (6) |
C6ii—C4—C5—C7 | 179.4 (4) | C8—C9—C13—C12 | −179.8 (4) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1iii | 1.05 (7) | 2.23 (6) | 2.897 (4) | 120 (5) |
N1—H1···O2iii | 1.05 (7) | 1.62 (7) | 2.609 (3) | 154 (5) |
Symmetry code: (iii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C20H14N22+·C6Cl2O42− |
Mr | 489.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 7.6279 (9), 8.4019 (10), 8.6291 (4) |
α, β, γ (°) | 97.171 (6), 99.673 (6), 95.728 (10) |
V (Å3) | 536.76 (9) |
Z | 1 |
Radiation type | Cu Kα |
µ (mm−1) | 3.05 |
Crystal size (mm) | 0.70 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.224, 0.750 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2340, 2187, 1213 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.161, 0.99 |
No. of reflections | 2187 |
No. of parameters | 182 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.29, −0.37 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1992), CAD-4 EXPRESS, HELENA (Spek, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 1.05 (7) | 2.23 (6) | 2.897 (4) | 120 (5) |
N1—H1···O2i | 1.05 (7) | 1.62 (7) | 2.609 (3) | 154 (5) |
Symmetry code: (i) −x, −y+1, −z. |
We have recently shown that the simple combination of chloranilic acid and dipyridyl-type ligands can create a variety of supramolecular architectures involving infinite one-dimensional molecular tape structures (Zaman et al., 1999, 2000). In the course of our crystal engineering studies on chloranilic acid, we have obtained the title compound, (I), a 1:1 co-crystal of chloranilic acid and 1,4-bis[(4-pyridyl)ethynyl]benzene. A long rigid and conjugated bridging ligand has received much current interest for the construction of self-assembling macrocyclic architectures (Lehn, 1995; Fujita, 1999) and the development of molecular wires (Tour, 1996). However, we have found only two examples (Lin et al., 1995, 1998) of the structures containing a 1,4-bis[(4-pyridyl)ethynyl]benzene unit in the Cambridge Structural Database (Allen & Kennard, 1993). We report here the structure of (I) with the hydrogen-bonded molecular tapes.
The molecular structure of (I) is shown in Fig. 1, and both molecules are located on the inversion center. A one-dimensional molecular tape is observed in the structure of (I), as shown in Fig. 2. The molecular tape is nearly flat. The angles between the molecular planes of the chloranilate and the pyridinium ring, and of the pyridinium ring and the benzene ring are 7.3 (2) and 11.8 (4)°, respectively. The molecular tapes are connected via R12(5) couplings with two intermolecular N—H···O hydrogen bonds (Table 1), where both H atoms of chloranilic acid have transfered to the pyridine rings. In previous work (Zaman et al., 2000), we have shown that the flat molecular tapes form segregated stacks of each molecule. However, the overlaps between the chloranilate–pyridinium ring–benzene ring–pyridinium ring–chloranilate are observed in the stacks of the molecular tapes of (I). A short C—Cl···π interaction [Cl1···(C7≡C8) 3.440 (7), Cl1···C7 3.503 (4), Cl1···C8 3.480 (4) Å; Cl1···C7≡C8 79.1 (3) and Cl1···C8≡C7 81.3 (3)°] exists between the stacks of the molecular tapes (Reddy et al., 1996; Prasanna & Row, 2000). It is 1.7% shorter than the sum of the van der Waals radii of Cl and Csp2 (Pauling, 1960).