Crystal Engineering through Halogen Bonding. 2. Complexes of

Department of Chemistry, Furman University, Greenville, South Carolina, 29613, and. Department of Chemistry, Hunter Chemistry Laboratories, Clemson ...
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Crystal Engineering through Halogen Bonding. 2. Complexes of Diacetylene-Linked Heterocycles with Organic Iodides April Crihfield,† Joshua Hartwell,† Dustin Phelps,† Rosa Bailey Walsh,‡ Jeffery L. Harris,‡ John F. Payne,‡ William T. Pennington,*,‡ and Timothy W. Hanks*,†

CRYSTAL GROWTH & DESIGN 2003 VOL. 3, NO. 3 313-320

Department of Chemistry, Furman University, Greenville, South Carolina, 29613, and Department of Chemistry, Hunter Chemistry Laboratories, Clemson University, Clemson, South Carolina 29634 Received January 9, 2003;

Revised Manuscript Received January 27, 2003

ABSTRACT: The bis(aryl)diacetylenes 1,4-bis(3-quinolyl)-1,3-butadiyne (1), 1,4-bis(4-isoquinolyl)-1,3-butadiyne (2), and 1,4-bis(3-pyridyl)-1,3-butadiyne (3) form strongly halogen bonded complexes with organic iodides, including tetraiodoethylene (TIE), 1,4-diiodotetrafluorobenzene (F4DIB), and 1,4-diiodooctafluorobutane (F8DIBut). The crystal structures for the new donor, 2, as well as for six complexes, 1‚TIE, 1‚F4DIB, 2‚TIE, 2‚F4DIB, 3‚(F4DIB)2, and 32‚ (F8DIBut)2, are reported. Extended chain structures consisting of donor and acceptor molecules are observed in all cases, except that of 32‚(F8DIBut)2, which forms a molecular adduct. In most cases, the complexes segregate into columns of donors and acceptors, as is typical for this class of complexes. However, 1‚F4DIB displays an unusual “crosshatched” pattern with each acceptor directly above the diacetylene moiety of another donor along the b-axis. In addition to 1‚F4DIB, 32‚(F8DIBut)2 also exhibits packing that does not consist of segregated stacks (i.e., the acceptor in the chain sits on top of one end of the donor and the uncomplexed F4DIB sits on top of the other end). Neither diacetylene 2, nor any of the complexes, pack in a manner that would allow for topotactic polymerization of the diacetylene moiety. Introduction Bis(aryl)diacetylenes are intriguing building blocks for supramolecular synthesis. They are rigid and planar, and a variety of systems can be easily synthesized from readily available components. The most widely investigated approach to supramolecular construction in these systems takes advantage of the fact that the diacetylene (DA) moiety has a strong tendency to stack into columnar arrays. If the packing of the arrays falls within certain empirically determined parameters (Figure 1), the DAs may undergo photoinduced topopolymerization.2 The resulting polymers are highly conjugated, deeply colored, and display interesting optical and nonlinear optical properties.2b In general, the polymerization reaction proceeds best when the DAs stack at a 45° angle from the long axis of the molecule. This puts the 1 and 4 positions of the DA moiety close enough to each other that atomic motion required on polymerization (Figure 1a) is minimized. These packing requirements are particularly strict with completely conjugated bis(aryl)diacetylenes, since their rigidity permits little motion during the polymerization reaction. A second packing motif has also been observed, where the DAs pack directly over one another.3 This presumably results in a head-to-head polymerization (Figure 1b). When the aryl groups are heterocycles, other types of supramolecular structures may be formed. For example, the heterocycle can act as a ligand to form coordination polymers. The linear compound 1,4-bis(4†

Furman University. Clemson University. * To whom correspondence should be addressed. [email protected]; [email protected]. ‡

Figure 1. Geometrical requirements for (a) head-to-tail and (b) head-to-head topopolymerization of DAs.

pyridyl)butadiyne has most often been used to form extended complexes with metals.4 However, there appear to be no examples of DA coordination polymers of this type that are capable of topopolymerization at the diacetylene.5 This is not surprising, as we are aware of only one symmetrical bis(heterocycle)DA, 1,4-bis(3quinolyl)-1,3-butadiyne, that photopolymerizes in the solid state.6 While it may be possible to use the coordination of a metal (or some other species) to manipulate the packing of the DAs into a more favorable geometry for DA polymerization, the formation of an extended chain structure would be expected to greatly restrict the motion of the reacting centers. This would increase the

10.1021/cg0340042 CCC: $25.00 © 2003 American Chemical Society Published on Web 02/22/2003

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Experimental Section

Figure 2. Diacetylene donor compounds 1-3.

strain that the crystal lattice would experience during the topopolymerization reaction, making the formation of crystalline polymers more challenging. This is unfortunate, since the resulting highly organized, threedimensional polymers would be of both theoretical and practical importance.7 While there are a number of examples of host-guest complexes formed from DAs attached to aliphatic carbons,8 reports of complexes built from crystals of bis(heterocyclic)DAs, where the heterocycle is in direct conjugation with the DA, are much less common. In one important example, Rodriquez methylated members of the bis(pyridyl)butadiyne family to give salts that are capable of forming π-π charge-transfer complexes with tetramethyl-p-phenylenediamine.9 Interestingly, quaternization of the pyridine nitrogen seems to encourage polymerization of the DA moiety (although not in any of the charge-transfer complexes). The reaction is not the topotactic 1-4 reaction described above, but a random radical polymerization to give a highly crosslinked material.10 We have long been interested in the halogen bonding interaction between N-heterocycles and organoiodides.1,11 Like hydrogen bonding, the halogen bond is a highly directional and relatively strong noncovalent bond. Nominally, the interaction involves the donation of the nitrogen lone pair into the C-I σ* antibonding orbital (a more detailed quantum mechanical description is available11c) and is therefore strengthened by electron withdrawing groups on the acceptor. While halogen bonding was first reported some 140 years ago,12 it has only recently been seriously investigated as a tool for crystal engineering.13 Herein we report the synthesis and structural characterization of a series of halogen-bonded complexes involving 1,4-bis(3-quinolyl)-1,3-butadiyne (1), its isomer 1,4-bis(4-isoquinolyl)-1,3-butadiyne (2), and 1,4-bis(3pyridyl)-1,3-butadiyne (3) (Figure 2). While DA 3 does not undergo ready solid-state photopolymerization, DA 1, which differs only in the addition of a fused benzene ring, does. DA 2 has not been previously reported. This compound is an isomer of 1 and retains the 1,3relationship between the nitrogen atom and the diacetylene. This paper looks for a simple relationship between DA molecular structure, DA crystal packing, and solidstate photoreactivity. In addition, we examine the influence of halogen bonding on the propensity of the DAs toward photopolymerization.

Materials and Methods. All reagents were purchased from Aldrich and were used as received. Solvents were purchased from commercial sources and distilled under argon from appropriate drying agents immediately before use. Carbon, hydrogen, and nitrogen analyses were performed by Atlantic Microlabs, Norcross, GA and were satisfactory for all compounds. Proton NMR data were collected at 500 MHz on a Varian INOVA 500 spectrometer and carbon-13 data were collected on a Varian VXR-300 spectrometer at 75 MHz. IR data were collected on a Nicolet Magna IR-750 Fourier Transform spectrometer. Melting point data were collected on at Mel Temp II apparatus and are uncorrected. Compounds 1 and 3 were prepared as previously reported, and their spectroscopic characterization was consistent with those reports.6,9 X-ray Crystallographic Studies. Specific details of the crystallographic experiment and results for each compound are given in Table 1. The data were measured at room temperature (295 ( 1 K) with graphite-monochromated Mo KR radiation (λ ) 0.71073 Å) on either a four-circle diffractometer (Nicolet R3mV or Rigaku AFC7R-18) with serial detection or on a three-circle diffractometer equipped with a CCD area detector (Rigaku AFC8/Mercury CCD). The data were corrected for Lorentz and polarization effects. The intensities of three reflections, remeasured periodically throughout data collection for 1‚TIE and 2‚TIE, declined by 9.6 and 4.8%, respectively. A linear correction was applied to the data for the latter two compounds to account for crystal decomposition. An absorption correction, based on either azimuthal scans of several intense reflections or on a multiscan technique,14 was applied to the data for each compound. All structures were solved by direct methods and refined (on F2) using full-matrix, least-squares techniques. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were either refined isotropically (compound 2) or were included in the structure factor calculation at optimized positions with isotropic displacement parameters fixed at values 20% greater than that of their host atom. Structure solution, refinement, and calculation of derived results was performed with the SHELXTL15 package of computer programs. Neutral atom scattering factors and the real and imaginary anomalous dispersion corrections were taken from International Tables for X-ray Crystallography, Vol. C.16 Synthesis of 2-Methyl-4-(4-isoquinolyl)but-3-yn-2-ol (4). To a 250 mL round-bottomed flask was added triethylamine (70 mL), 2-methylbut-3-yn-2-ol (3.36 g, 0.040 mol), 4-bromoisoquinoline (4.16 g, 0.020 mol), and tetrakis(triphenylphosphine)palladium (0.50 g, 1.1 mmol). The flask was flushed with dry N2 and a solution containing CuBr (0.20 g, 1.4 mmol) and LiBr (0.7 g, 8.1 mmol) in 10 mL of anhydrous THF was added with stirring. The mixture was heated at reflux under dry N2 for 3 h, cooled to room temperature, and the inorganic salts removed by vacuum filtration. The triethylamine was removed under vacuum. Water was added to the crude product, and the resulting solution was extracted with diethyl ether. The organic layer was dried with MgSO4, and the product was recrystallized from ethyl acetate/hexane to give white needles (85%), mp 107-108 °C. 1H NMR (500 MHz, CDCl3) δH 1.78 (s, 6H), 7.66 (dd, 1H), 7.79 (dd, 1H), 7.98 (d, 1H), 8.19 (d 1H), 8.68 (s, 1H), 9.19 (s, 1H). Synthesis of 4-Isoquinoylacetylene (5). Toluene (300 mL), finely ground NaOH (5 g), and 4 (4.22 g, 0.020 mol) were placed in a 500 mL round-bottom flask and heated to reflux under nitrogen for 5 h. The mixture was filtered and the toluene was removed under vacuum. The crude product was dissolved in diethyl ether and washed with water. The organic layer was dried with MgSO4 and the product was recrystallized from ethyl acetate/hexane to give a pale yellow solid (80%), mp 79-80 °C. 1H NMR (500 MHz, CDCl3) δH 3.55 (s, 1H), 7.66 (dd, 1H), 7.80 (dd, 1H), 7.95 (d, 1H), 8.26, (d, 1H), 8.73 (s, 1H), 9.21 (s, 1H). Synthesis of 1,4-Bis(4-isoquinolyl)-1,3-butadiyne (2). A solution of CuCl (198 mg, 2.0 mmol), 5 (1.53 g, 0.010 mol), and TMEDA (2 mL) in 35 mL of DME was stirred rapidly as

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Table 1. Crystal Data for 1‚TIE, 1‚F4DIB, 2,2‚TIE, 2‚F4DIB, 32‚F8DIBut, and 3‚(F4DIB)2 1‚TIE formula Mw crystal color, habit crystal dimensions (mm) crystal system space group a, Å b, Å c, Å R, (°) β, (°) γ, (°) V, Å3 Z Dcalc, g cm-3 diffractometer θrange (°) µ, mm-1 transmission coefficients reflections collected reflections unique (Rint) reflections observed (I > 2σ(I)) R1a wR2b

1‚F4DIB

C24H12N2I4 835.96 light-yellow, needle 0.12 × 0.14 × 0.28

C28H12N2F4I2 706.20 light-blue, needle 0.07 × 0.07 × 0.43

triclinic P1 h (no. 2) 7.1360(5) 8.9258(7) 10.2314(7) 95.699(5) 108.631(5) 91.813(6) 613.09(8) 1 2.26 Siemens R3mV 2.11-27.57 5.10 0.73-1.00

2 C22H12N2 304.34 yellow, needle

2‚TIE

2‚F4DIB

3‚(F4DIB)2

32‚F8DIBut

0.10 × 0.10 × 0.60

C24H12N2I4 835.96 light-yellow, needle 0.12 × 0.22 × 0.41

C28H12N2F4I2 706.20 light-yellow, plate 0.11 × 0.24 × 0.36

C26H8N2F8I4 1007.94 light-yellow, needle 0.11 × 0.12 × 0.36

C32H16N4F8I2 862.29 yellow, parallelepiped 0.07 × 0.19 × 0.48

monoclinic C2/c (no. 15) 19.293(4) 9.546(2) 15.771(3)(7) 90 121.770(6) 90 2469(1) 4 1.90 Rigaku AFC8/ Mercury CCD 2.47-26.73 2.60 0.67-1.00

monoclinic P21n (no. 14) 3.816(2) 25.504(13) 7.767(4) 90 93.988(9) 90 754.0(6) 2 1.34 Rigaku AFC8/ Mercury CCD 2.75-25.67 0.079 0.77-1.00

triclinic P1h (no. 2) 7.362(1) 19.278(4) 4.2134(5) 94.07(1) 98.13(1) 97.22(1) 584.9(2) 1 2.37 Rigaku AFC7R-18 2.14-27.48 5.34 0.57-1.00

triclinic P1h (no. 2) 4.023(2) 7.540(4) 20.239(11) 80.97(3) 85.29(4) 84.00(3) 601.6(5) 1 1.95 Rigaku AFC8/ Mercury CCD 2.78-26.37 2.66 0.54-1.00

triclinic P1 h (no. 2) 7.479(2) 11.186(2) 17.454(4) 81.880(14) 87.58(2) 79.740(12) 1422.2(6) 2 2.35 Rigaku AFC8/ Mercury CCD 2.80-26.50 4.45 0.61-1.00

monoclinic P21/c (no. 14) 18.7594(5) 7.2538(11) 12.0581(9) 90 101.7708(10) 90 1606.3(3) 2 1.78 Rigaku AFC8/ Mercury CCD 3.33-26.37 2.03 0.66-1.00

3067

11368

4390

2909

5574

13885

23586

2843 (0.015)

2534 (0.032)

1426 (0.046)

2869 (0.029)

2334 (0.157)

5784 (0.047)

3252 (0.034)

2399

2484

1153

2660

1902

4887

3251

0.0246 (0.0311) 0.0609 (0.0622)

0.0492 (0.0530) 0.0861 (0.0869)

0.0856 (0.1033) 0.1345 (0.1420)

0.0599 (0.0693) 0.1514 (0.1555)

0.1471 (0.1633) 0.2818 (0.2916)

0.0671 (0.0812) 0.1362 (0.1454)

0.0469 (0.0801) 0.1076 (0.1260)

a R ) Σ||F | - |F ||/ Σ|F | for observed data (I > 2σ(I)); number in parentheses is for all data. b wR ) {Σ[w(F 2 - F 2)2]/Σ[w(F 2)2]}1/2 1 o c o 2 o c o for observed data (I > 2σ(I)); number in parentheses is for all data.

Figure 3. Synthesis of diacetylene donor 2. O2 was bubbled through it. After 3 h, the solvent was removed and the solid was extracted with chloroform, washed with water, and dried of MgSO4. The product was then recrystallized from chloroform to give a yellow solid (40%), mp 242243. 1H NMR (500 MHz, CDCl3) δH 7.72 (dd, 2H), 7.86 (dd, 2H), 8.04 (d, 2H), 8.34, (d, 2H), 8.84 (s, 2H), 9.26 (s, 2H). Preparation of Charge-Transfer Complexes, General Procedure. Equal molar amounts of the diacetylene donor and either tetraiodoethylene (TIE) or 1,4-diiodotetrafluorobenzene (F4DIB) were dissolved in methylene chloride. Slow evaporation of the solvent gave crystalline solids suitable for single-crystal analysis.

Results and Discussion Synthesis and Photostability of Diacetylene Donors. The diacetylene donors were prepared by the classic route shown in Figure 3. Donors 1 and 3 have been previously reported, while the isoquinoline derivative 2 is a new compound. The route involves the Sonogashira coupling17 of a protected acetylene to an

aryl halide. Base-catalyzed deprotection followed by a copper-catalyzed oxidative coupling gives the corresponding diacetylene in good yields. As previously noted, 1 is light sensitive, photopolymerizing slowly in ambient light to form a blue solid. This compound was stored cold and in the dark. Fortunately, the polymer is completely insoluble and the inevitable slight contamination of the monomer did not interfere with the preparation of charge-transfer complexes. Donors 2 and 3 did not undergo solid-state polymerization even when irradiated with intense UV light for a period of days. Thus, it seems that neither the relative location of the DA to the nitrogen nor the presence of a fused ring systems are sufficient for solid-state photopolymerization. Structure Discussion of Complexes. All of the compounds crystallize with significant halogen bonding between the organoiodide acceptor and the nitrogen heterocycle donor to form either extended chain structures, or in the case of 32‚F8DIBut, a molecular adduct. In all complexes involving 2, the chains are oriented to give segregated stacks of donors and acceptors with no significant interaction between adjacent members of a stack. More varied interaction is seen with complexes involving 1 and 3. Although many of the donor diacetylene molecules are within the required contact distance for solid-state polymerization, none are at the proper stacking angle to provide the slipped-stack necessary for this phenomenon. Selected bond distances and angles for halogen bonding between the donor and acceptor and for the diacetylene moiety are given in Table 2. Crystal Structure of 1‚TIE. Molecules of 1 and TIE, shown in Figure 4, are each situated about inversion

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Table 2. Selected Distances (Å) and Angles (°)a Donor‚Acceptor Parameters compound

(a) N‚‚‚I (Å)

(b) N‚‚‚I-C (°)

(c) I‚‚‚N-C (°)

119

117.4(6) 117.3(2)

320 F4DIB21 TIE11b

1‚TIE 1‚F4DIB 2 2‚TIE 2‚ F4DIB 3‚(F4DIB)2 32‚F8DIBut

(e) C-Xb (Å)

(d) C-N-C (°)

2.884(3) 2.916(4)

174.75(11) 168.37(15)

125.80(19), 115.9(2) 132.3(3), 109.1(3)

2.949(11) 2.913(15) 2.895(9) 2.913(9) 2.858(4)

175.4(5) 176.6(6) 174.4(3) 172.4(3) 174.9(3)

129.8(9), 114.5(9) 128.3(14), 113.2(13) 126.9(8), 114.9(7) 127.2(8), 115.2(7) 129.3(3), 111.9(3)

118.3(3) 118.4(4) 116.8(3) 115.4(12) 118.3(18) 118.1(10) 117.6(10) 117.4(4)

2.075(8) 2.095(14) 2.100(16) 2.112(16) 2.164(22) 2.115(3), (2.104(4)) 2.096(4) 2.086(11), (2.080(13)) 2.103(18) 2.094(10), 2.086(9) (2.083(11)), (2.070(11)) 2.156(2)

Diacetylene Parameters compound 119 320 1‚TIE 1‚F4DIB 2 2‚TIE 2‚ F4DIB 3‚(F4DIB)2 32‚F8DIBut a

(f) C-C (Å)

(g) C≡C (Å)

(h) C-C (Å)

(i) Cf-C≡C (°)

(j) C≡C-Ch (°)

1.431(3) 1.442(8) 1.431(4) 1.433(6) 1.431(4) 1.422(18) 1.44(3) 1.372(16) 1.422(14) 1.431(6)

1.199(3) 1.192(7) 1.192(5) 1.192(5) 1.193(7) 1.211(18) 1.18(3) 1.177(15) 1.173(15) 1.195(6) 1.197(6)

1.371(3) 1.369(11) 1.375(6) 1.375(6) 1.366(9) 1.38(3) 1.41(4) 1.425(15)

178.1(2) 178.4(6) 177.2(4) 177.2(4) 177.2(4) 175.5(16) 175(2) 176.4(14) 177.0(13) 179.7(5) 178.4(6)

179.7(2) 178.7(7) 179.3(5) 179.3(5) 179.3(5) 176(2) 177(3) 177.8(13) 175.8(14) 178.7(5)

1.376(7)

Distances and angles refer to the figure below. b Atom labels with a subscripted letter also refer to this figure.

Figure 5. Crystal packing of 1‚TIE, viewed down the a-axis.

Figure 4. Thermal ellipsoid plot (50% probability) of 1‚TIE (symmetry related atoms are generated by operations listed in Table 2).

centers: the TIE molecule at the origin and the diacetylene at (1 2 1). The two are linked by halogen bonding into zigzag chains that run along the (1 2 1) direction. The donor and acceptor molecules are both planar (rms deviations of 0.0028 and 0.0657 Å, respectively) and are nearly orthogonal (dihedral angle of 72.66(2)°). Chains stack along the a-axis (Figure 5) with neighboring chains related by inversion centers: (0 1/2 1/2) and (1/2 1/2 1/2), with heterocycle interplanar spacings of

3.42(2) and 3.28(2) Å, respectively. The general packing of the TIE molecules is similar to that observed in many halogen-bonded complexes of this acceptor,11b but whereas those complexes are dominated by I‚‚‚I interactions there are no such close contacts in this complex. Crystal Structure of 1‚F4DIB. Donor and acceptor molecules, shown in Figure 6, are both situated about inversion centers: the F4DIB molecule at (1/4 3/4 1/2) and the diacetylene at (-1/4 1/4 0). The two are linked by halogen bonding into zigzag chains that run along the body diagonal ((1 1 1) direction). The donor and acceptor molecules are both planar (rms deviations of 0.0184 and 0.0489 Å, respectively) and are nearly orthogonal (dihedral angle of 86.70(5)°). Chains are

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Figure 9. Crystal packing of 2, viewed down the a-axis.

Figure 6. Thermal ellipsoid plot (50% probability) of 1‚F4DIB (symmetry related atoms are generated by operations listed in Table 2).

Figure 10. Thermal ellipsoid plot (50% probability) of 2‚TIE (symmetry related atoms are generated by operations listed in Table 2).

Figure 7. Crystal packing of 1‚F4DIB, viewed down the b-axis.

Figure 11. Crystal packing of 2‚TIE, viewed down the c-axis.

Figure 8. Thermal ellipsoid plot (50% probability) of 2 (symmetry related atoms are generated by operations listed in Table 2).

oriented such that the acceptor is situated directly above the center of the diacetylene moiety along the b-axis (Figure 7). Crystal Structure of 2. Molecules of 2, shown in Figure 8, are planar to within 0.0528 Å. The molecule is situated about an inversion center (1/2 1/2 1/2) and stack along the a-axis with adjacent molecules in the stack related by translation and separated by an inter-

planar spacing of 3.56(5) Å. Weak C-H‚‚‚N interactions (H‚‚‚N ) 2.48(3) Å; C‚‚‚N ) 3.499(5) Å; C-H‚‚‚N ) 165(3)°) join molecules along the (1 1 1) direction (see Figure 9). Crystal Structure of 2‚TIE. Molecules of 2 and TIE, shown in Figure 10, are each situated about inversion centers: the TIE molecule at the origin and the diacetylene at (0 1/2 1/2). The two are linked by halogen bonding into zigzag chains that run along the (0 1 1) direction. The donor and acceptor molecules are both planar (rms deviations of 0.0004 and 0.0609 Å, respectively), but are closer to parallel than to orthogonal (dihedral angle of 35.85(13)°). Chains stack along the c-axis (Figure 11) with neighboring chains related by translation. The general packing is similar to that observed in many halogen-bonded complexes of this acceptor,11b with I‚‚‚I interactions of 3.8692(19) and

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Crystal Structure of 2‚F4DIB. Molecules of 2 and F4DIB, shown in Figure 12, are situated about inversion centers of (0 0 1/2) and (1/2 1/2 0), respectively. Halogen bonding links them into extended chains which run in the (1 1 1) direction. Both the donor and acceptor molecules are planar (rms deviations of 0.0071 and 0.0600 Å, respectively) with a dihedral angle between them of 14.2(8)°. As in 2‚TIE, the complex crystallizes in a manner very similar to the donor, 2,18 with extended chains of alternating donors and acceptors, which are positioned to give segregated stacks of donors and acceptors (see Figure 13) running along the shortest unit cell axis (a). The interplanar spacing for the F4DIB acceptors is 3.579(8) Å and for the donors the spacing is 3.65(6) Å.

Figure 12. Thermal ellipsoid plot (50% probability) of 2‚ F4DIB (symmetry related atoms are generated by operations listed in Table 2).

Figure 13. Crystal packing of 2‚F4DIB, viewed down the a-axis.

Figure 14. Thermal ellipsoid plot (50% probability) of 3‚(F4DIB)2 (symmetry related atoms are generated by operations listed in Table 2).

4.1486(14) Å. As has been previously noted, this packing is quite similar to the packing of TIE itself, but it should be pointed out that this is also quite similar to the packing of 2, with the TIE molecule taking the place of alternating diacetylene molecules of the C-H‚‚‚N linked chains.

Crystal Structure of 3‚(F4DIB)2. The complex of 3 with F4DIB includes an additional uncomplexed molecule of the latter, and all three molecules sit on general positions within the unit cell (see Figure 14). The diacetylene donor, the F4DIB acceptor, and the additional F4DIB molecule are planar (rms deviations of 0.0289, 0.0024, and 0.0146 Å, respectively) and are nearly parallel, with a dihedral angle of 3.5(3)° between the donor and acceptor and dihedral angles to the uncomplexed molecule of 4.2(3)° for the donor and 7.8(4)° for the acceptor. Pairs of zigzag X-bonded chains related by inversion symmetry at the origin stack along the a-axis. This results in stacks of alternating complexed F4DIB molecules and pyridyl rings from one end of the donor (atoms N2 and C22-C26). The interplanar spacings for this stack are 3.45(5) and 3.50(5) Å. The uncomplexed F4DIB molecule forms alternating stacks with the other end of the diacetylene molecule (N1 and C13-C17) with interplanar spacings of 3.50(9) and 3.63(8) Å. The crystal packing is shown in Figure 15. 32‚F8DIBut. The bulkier F8DIBut acceptor crystallizes with two molecules of 3 (see Figure 16). As only one end of the diacetylene is X-bonded to the acceptor a molecular adduct is formed rather than an extended chain. The diacetylene donor is planar (rms of 0.0423 Å), and the donors of adducts related by a 21 screw operation (about 1/2 y 1/4) are interdigitated to form stacks up the b-axis (shown in Figure 17). The interplanar spacings between donors in the stack are 3.6(1) and 3.7(1) Å. It is interesting to note that, unlike all the other donors which possess crystallographic or local inversion symmetry, the molecule of 3 in this complex does not (i.e., both nitrogen atoms are on the same side of the plane parallel to the diacetylene group and bisecting the pyridine rings).

Figure 15. Crystal packing of 3‚(F4DIB)2, viewed down the a-axis.

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Crystal Growth & Design, Vol. 3, No. 3, 2003 319 Supporting Information Available: X-ray crystallographic information file (CIF) for all seven complexes. This material is available free of charge via the Internet at http:// pubs.acs.org.

References

Figure 16. Crystal packing of 32‚F8DIBut, viewed down the b-axis.

Figure 17. Thermal ellipsoid plot (50% probability) of 32‚ F8DIBut (symmetry related atoms are generated by operations listed in Table 2).

Conclusions Halogen bonding between bis(N-heterocycle)DAs 1-3 and various organoiodide acceptors generally leads to extended chain structures ordered into stacks of donors and acceptors perpendicular to the chains. With one major and one minor exception, the general structural motifs observed here are closely related to previously reported structures of other halogen bonded complexes involving planar bis(heterocycle) donors. While the stacking of DA donors can be engineered using planar organoiodide acceptors, it is clear that this simple approach is not sufficient to reliably produce geometries suitable for the topopolymerization of the DAs. In future papers, we will discuss the use of other supramolecular synthons, particularly the use of flexible “BCMU” tail groups on unsymmetrical DAs, for fine-tuning the stacking geometry of halogen bonded DAs. Acknowledgment. Financial support by ACS-PRF (Grant No. 35462-B5), and the National Science Foundation (Grant Nos. CHE-0203402, research; CHE0138535, Furman University REU; ESR-9108772 and CHE-9207230, Clemson University X-ray instrumentation) are gratefully acknowledged.

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