Conflicting Behavior of a Versatile Host Compound: X-ray Crystal

Dec 22, 2009 - the solvent-free host compound 1 as well as the crystal. Scheme 1. .... Figure 3. Packing diagram of 1 viewed down the crystallographic...
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DOI: 10.1021/cg901217k

Conflicting Behavior of a Versatile Host Compound: X-ray Crystal Structures Arising from Solvent-free and Solvent-Containing Crystal Formation†

2010, Vol. 10 862–869

Konstantinos Skobridis,‡ Vassiliki Theodorou,‡ Wilhelm Seichter,§ and Edwin Weber*,§ ‡

Department of Chemistry, University of Ioannina, GR-451 10 Ioannina, Greece and §Institut f€ ur Organische Chemie, Technische Universit€ at Bergakademie Freiberg, Leipziger Strasse 29, D-09596 Freiberg/Sachsen, Germany Received October 5, 2009; Revised Manuscript Received November 12, 2009

ABSTRACT: The X-ray crystallographic structures of four new inclusion compounds of the versatile clathrate host 2,20 -bis(9hydroxy-9-fluorenyl)biphenyl (1) as well as the crystal structure of the unsolvated host are reported and comparatively discussed with regard to the molecular conformation and the modes of interactions the molecules make use of in the crystal packing. While the inclusion crystals demonstrate full saturation of the hydrogen bond capacity of the host molecule, 1 is only involved in weak intermolecular π-contacts in the solvent-free structure. We draw the conclusion that the well-tried strategy of coordinatoclathration, underlying the present inclusion compounds, should not be regarded as a strict rule with reference to the formation of inclusion crystals but a helpful framework in the search of new efficient clathrate hosts.

Introduction Organic compounds having a strong tendency for a cocrystallization with other organic molecules are of great interest in view of various scientific and practical aspects, including crystal engineering,1 compound separation2 and compound storage,3 solid state reactions,4 or other particular fields of materials science.5-8 Compounds being endowed with this salient property are generally referred to as a “versatile clathrate host”,9 giving inclusion compounds with a great variety of relatively small organic guest molecules such as organic solvents.10 Host-guest compounds of this type date back to the beginning of the 19th century11 and have been discovered at the early time of clathrate chemistry, in most cases accidentally.12 These nonengineered host-guest compounds posed a challenge to develop some rational design strategy of host frameworks, the structure of which is largely guest intensive.13 One of the keynote features of a corresponding design strategy is the shape awkwardness of the host molecule rendering close-packing difficult in the crystal lattice.14 This is produced by bulky residues of the host material. Additional functional groups that can only hardly contact the function of a neighboring host molecule but more easily a complementary smaller guest molecule are characteristic of the strategy of “coordinato-clathration”.15 Very often the functional group of the coordinato-clathrate host is capable of hydrogen bonding to the guest molecule. A typical case of such an engineered coordinato-clathrate host is the diol 2,20 bis(9-hydroxy-9-fluorenyl)biphenyl (1) (Scheme 1), giving rise to a great number and range of crystalline inclusions and thus being termed with good reason a “versatile host compound”.16 Considering this concept, the host molecule should have a high infinity for a guest molecule when forming a crystal structure, while the packing of the apohost may prove

problematic due to low packing coefficients. Actually, this is true since crystal structures of neat host compounds, being otherwise largely guest intensive, are hardly known in the literature.17 However, as shown with the present paper, the above relation may not be taken as a strict rule but rather as a helpful guideline. Hence, we report on the crystal structures of four new inclusion compounds of 1 (1a-1d), Scheme 1) that involve guests of very different functionality (proton donor and acceptor compounds of varied polarity), illustrating again the versatility of host behavior but also describing the crystal structure of the neat host compound 1 which is now successfully managed. Moreover, we give notice that 1d (1 3 dioxane 3 acetonitrile) is the first example of a three-component (mixed guest) inclusion crystal of 1. Results and Discussion X-ray Single-Crystal Structures. The crystal structure of the solvent-free host compound 1 as well as the crystal Scheme 1. Compounds Studied in This Paper

† Dedicated to Professor Luigi Nassembeni on the occasion of his 70th birthday. *To whom correspondence should be addressed. E-mail: edwin.weber@ chemie.tu-freiberg.de; fax: (þ49) 3731-39 3170.

pubs.acs.org/crystal

Published on Web 12/22/2009

r 2009 American Chemical Society

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Figure 1. Conformation, atom numbering, and plane specification scheme of the molecule 1. The torsion angle τ1 is depicted as a dotted line, and τ2 and τ3 are specified as dashed lines.

Figure 3. Packing diagram of 1 viewed down the crystallographic a-axis. With the exception of the hydroxyl hydrogens, all other hydrogen atoms are omitted for clarity. Broken lines represent hydrogen bond type contacts. The two crystallographically independent host molecules are distinguished in bold and light fashion.

Figure 2. ORTEP plot showing the asymmetric unit of the crystal structure of the solvent-free compound 1. Thermal ellipsoids are drawn at the 40% probability level. Broken single lines represent O-H 3 3 3 O hydrogen bonds, and the broken double line represents a O-H 3 3 3 π interaction.

structures of four inclusion compounds of 1, namely, 1 3 phenyl acetate (1:1) (1a), 1 3 cyclohexanol (1:2) (1b), 1 3 1,4-dioxane (2:3) (1c), and 1 3 1,4-dioxane 3 acetonitrile (1:1:1) (1d), has been studied by X-ray diffraction analysis. We note at this point that not only is the structure of the neat host compound 1 (free from solvent) a singular case but so is the structure of the inclusion compound 1d containing two different solvents (1,4-dioxane and acetonitrile) in the crystal lattice. A scheme specifying the conformation and the atom numbering of molecule 1 is given in Figure 1. Molecular illustrations of 1 and 1a-1d are presented in Figures 2, 4, 6, 8, and 10, while the packing diagrams are shown in Figures 3, 5, 7, 9, and 11, respectively. Crystallographic data, selected conformational parameters, and information about hydrogen bond interactions are listed in Tables 1-3, respectively. Basic Structure Description of the Host Molecule. The conformation of the host molecule 1 can be described by a set of three torsion angles (Figure 1). Those which are given by the atomic sequences O(1)-C(13)-C(14)-C(19) and C(20)-C(25)-C(26)-O(2), denoted as τ2 and τ3, describe the orientation of the fluorenyl moieties with respect to the phenyl rings to which they are attached, while τ1 [C(14)-C(19)-C(20)-C(25)] defines the torsion angle between the aromatic rings of the central biphenyl unit. In the

crystal structures of 1 and 1a-1d, the host molecule adopts a helical conformation, which is stabilized by a strong intramolecular hydrogen bond between the hydroxy groups [d(O(2) 3 3 3 O(1) 2.661(2)-2.837(3) A˚], which is also present in all previous structures involving this16 and related host compounds.18 Although the central phenylene rings are always arranged nearly orthogonal to each other, as approximated by the torsion angle τ1 in Figure 1 [91.3(5)-94.9(2)°], the torsion angles τ2 and τ3 range from 12.6(4) to 29.3(4) and 12.2(2) to 33.4(4)°, respectively, indicating rather high conformational freedom of the fluorenyl moieties with regard to their adjacent phenylene rings. Crystal Structure Description. Compound 1. Slow evaporation of a solution of 1 in chlorocyclohexane gave rise to the formation of solvent-free crystals. This seems reasonable insofar as chlorocyclohexane is a molecule hardly showing readiness to hydrogen bonding. In the crystal structure of the free host 1, the asymmetric entity of the unit cell (space group P21/c) contains two crystallographically independent molecules (Figure 2) with different conformations around their biphenyl parts, which is also evident from the geometrical parameters listed in Table 2. In one of the molecules, the hydroxy hydrogen, exclusive of the O-H 3 3 3 O bonding, forms a relatively strong O-H 3 3 3 π(arene) contact19 [O(1A)-H (1A) 3 3 3 C(23A) 2.34 A˚, 172.5°] to an adjacent molecule, while in the second molecule this hydrogen is located above an aromatic ring, thus creating a weak intramolecular contact [O(1)-H(1) 3 3 3 centroid(ring D) 2.99 A˚, 131.2°]. According to the aromatic nature of the molecular backbone, the packing structure of 1 (Figure 3) is stabilized by a close network of CH/π contacts20 (Table 3) and to a lesser degree by offset face-to-face interactions21 with a centroid-to-centroid distance of 3.8 A˚ between aromatic rings. Although the contribution of a single CH/ π interaction is rather small, the interplay of a large number

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Figure 6. ORTEP plot of the inclusion compound 1b. Thermal ellipsoids are drawn at the 40% probability level. Broken lines represent hydrogen bonds.

Figure 4. ORTEP plot of the inclusion compound 1a. Thermal ellipsoids are drawn at the 40% probability level. Broken single lines represent O-H 3 3 3 O hydrogen bonds, and the broken double line represents a O-H 3 3 3 π interaction.

Figure 5. Packing motif of the inclusion compound 1a. Broken single lines represent hydrogen bonds, and broken double lines represent O-H 3 3 3 π interactions.

of these interactions, as in the present case, produces a decisive factor for the stabilization of the crystal lattice. Compound 1a. Crystallization of 1 from phenyl acetate yields the 1:1 host-guest complex 1a, the molecular structure of which is displayed in Figure 4. The crystal structure belongs to the space group P21/n with the asymmetric cell unit containing one diol and one molecule of phenyl acetate. In this complex, the guest molecule appears to be fixed in its position by an intermolecular hydrogen bond [O(1)-H(1) 3 3 3 O(2G) 2.01 A˚, 159.4°] and a weak CH/π contact with the arene ring of the guest acting as an acceptor [C(29)-H(29) 3 3 3 centroid 2.84 A˚, 156.7°]. In addition, the hydrogens H(2G), H(4G), and H(6G) of phenyl acetate are linked further to three neighboring host molecules via C-H 3 3 3 O and CH/π contacts. Obviously, the high degree of intermolecular cross-linking determines the conformation of the guest molecule such that the acetate fragment is inclined at an angle of 69.5(1)° with respect to the aromatic ring. The crystal structure is composed of chainlike hydrogen bonded host-guest aggregates with an alternating order of host and guest molecules (Figure 5).

Compared with the solvent-free structure of 1, the presence of the guest molecule in 1a markedly reduces the degree of host-host interactions. Compound 1b. The crystalline 1:2 host/guest inclusion compound with cyclohexanol 1b was obtained on crystallization from this solvent. The intensity statistics, obtained from direct methods, indicate that the inclusion compound crystallizes in the noncentrosymmetric space group Pc. The asymmetric entity of the unit cell contains two crystallographically independent host molecules and four molecules of cyclohexanol (Figure 6), which form a continuous O-H 3 3 3 O hydrogen bond system [d(O 3 3 3 O) 2.646(3)2.900(4) A˚]. The host oxygen O(1) is weakly coordinated to an adjacent guest molecule via an inverse bifurcated C-H 3 3 3 O hydrogen bond [C(1I)-H(1I1) 3 3 3 O(1) 2.64, 139.3°; C(3I)-H(3I2) 3 3 3 O(1) 2.53 A˚, 141.6°], whereas the hydroxy hydrogen H(1I) of this particular guest, surpisingly enough, does not participate in hydrogen bonding. Packing effects cause a slight bend of one fluorenyl residue of each host molecule with a maximum atomic distance of 0.21 (0.19 A˚) from the least-squares plane of the aromatic unit. As mentioned above, the crystal structure of 1b is composed of O-H 3 3 3 O bonded 2:4 host-guest units, which in turn are associated among each other by weaker hydrogen bonding contacts. The high content of crystal solvent prevents effective arene-arene interactions, which are restricted to only one CH/π contact per host molecule (Figure 7). Compound 1c. The host 1 yields a 2:3 inclusion compound with 1,4-dioxane 1c of the space group P1 when crystallized from the same solvent. The stoichiometric unit of the inclusion structure is shown in Figure 8. All dioxane molecules adopt an undistorted chair conformation. Because of the presence of a host intramolecular hydrogen bond, only two of the guest molecules are coordinated to a host molecule by a conventional hydrogen bond [O(1)-H(1) 3 3 3 O(1F) 1.79 A˚, 178.9°; O(1A)-H(1A) 3 3 3 O(1G) 1.84 A˚, 175.4°]. Moreover, the oxygen O(1G) is involved in a weaker hydrogen bond [C(37A)-H(37A) 3 3 3 O(1G) 2.76 A˚, 137.6°]. The remaining oxygens take part in host-guest associations via C-H 3 3 3 O contacts with H 3 3 3 O distances ranging between 2.53 and 2.76 A˚. The different binding modes of the guest molecules imply differences regarding their molecular environment. In the crystal packing of 1c, which is illustrated in Figure 9,

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Figure 7. Packing diagram of the inclusion compound 1b. Only the hydrogens involved in hydrogen bonding (broken lines) are displayed. The two crystallographically independent host molecules are distinguished in bold and light fashion. Figure 9. Packing structure of 1c viewed down the crystallographic a-axis. With the exception of the hydroxy hydrogens, all other hydrogen atoms are omitted for clarity. Broken lines represent hydrogen bonds. The two crystallographically independent host molecules are distinguished in bold and light fashion.

Figure 8. ORTEP plot of the inclusion compound 1c. Thermal ellipsoids are drawn at the 40% probability level. Broken lines represent hydrogen bond type contacts.

pairs of the solvent molecules, which are connected to the host functional groups, are accommodated in closed cavities each created by the aromatic parts of six host molecules. The remaining guests are located in channel-like voids extending along the a-axis. It should be mentioned that these channels have an irregular cross-section with characteristic constrictions, which allow a tight fit of the incorporated guest molecule. Compound 1d. Crystallization of 1 from a solvent mixture 1,4-dioxane/acetonitrile yielded colorless prisms which proved to be an inclusion compound 1d (space group P21/c, Z = 4) containing the solvents 1,4-dioxane and acetonitrile with a host/guest stoichiometric ratio of 1:1:1. The dioxane molecule is hydrogen bonded to the host molecule [O(1)-H(1) 3 3 3 O(1G) 1.93 A˚, 166.7°], while the O(2G) of this guest is linked to the arene hydrogen of another host molecule [C(34)-H(34) 3 3 3 O(2G) 2.69 A˚, 154.1°]. One of the protic methyl hydrogens of the acetonitril molecule is linked via C-H 3 3 3 O bonding to O(2) of the diol host [d(H 3 3 3 O) 2.50 A˚], while a second methyl hydrogen is linked to the nitrogen of a neighboring acetonitrile [C(2H)-H(2H1) 3 3 3 N(1H) 2.55 A˚, 149.8°], resulting in infinite

C-H 3 3 3 N bonded19,22 zigzag strands (Figure 10). The crystal structure of 1d is stabilized by a complex three-dimensional supramolecular network, which includes O-H 3 3 3 O, C-H 3 3 3 O, and C-H 3 3 3 N hydrogen bonds and comprises host-guest and guest-guest interactions, while the host lattice is dominated by CH/π contacts and offset face-to-face interactions between aromatic groups. A view of the packing structure in the direction of the crystallographic c-axis (Figure 11) reveals that the guest molecules reside in parallel channels which are separated by the fluorenyl groups of the host molecules. According to the steric requirements of the guest species, the channels incorporating the acetonitrile have a nearly quadratic cross section, whereas those containing the dioxane molecules have an elongated profile. Conclusions In a way, a conflict situation is being manifested by the crystal structures reported in the present paper. On the one hand, four new inclusion structures of 2,20 -bis(9-hydroxy-9fluorenyl)biphenyl (1) underscore the versatile clathrate behavior of the particular host compound,16 which is in accordance with the key elements of the “coordinato-clathrate strategy”; that is, the awkwardness of the molecular shape and host functional groups make it difficult for them to contact each other.15 This is demonstrated with the inclusion compounds 1a-1d, enabling both the host and guest molecules to exercise their full or almost full hydrogen bond capacity depending on the particular structure of the guest. At a close look, in 1a, the carbonyl oxygen of the strong acceptor molecule phenyl acetate provides satisfaction for the free hydroxyl function of the host molecule. Moreover, as a special feature of this guest molecule, its aromatic moiety shows distinct participation in the host-guest interaction via C-H 3 3 3 O19 and C-H 3 3 3 π20 contacts. Another structural situation, still being in mutual agreement with the host concept, is found in the inclusion compound 1b. Here, the host and the cyclohexanol guest molecules assemble to form a

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Figure 10. Structure motif of the inclusion compound 1d. With the exception of the hydroxy hydrogens, all other hydrogen atoms of the host molecule are omitted for clarity. Oxygens are displayed as dotted, and nitrogens are displayed as hatched circles. Hydrogen bond type interactions are specified as broken lines. Molecules in bold style represent the stoichiometric unit.

hydrogen bonded 2:4 host-guest aggregate enabling full saturation of the hydroxyl groups except the terminal positions of the aggregate. As was to be expected from the 2:3 host/ guest stoichiometric ratio (two hydrogen donors and three hydrogen acceptors) in the 1,4-dioxane inclusion compound 1c, one of the 1,4-dioxane molecules cannot be included in a strong O-H 3 3 3 O hydrogen bond but only in a much weaker contact of C-H 3 3 3 O fashion, thus giving the structure the character of a kind of hybrid between “coordinato-clathrate” and “true clathrate”. In a strict sense, these two terminologies have been introduced to distinguish between clathrate systems that are based on a strong coordinative host-guest interaction such as conventional hydrogen bonding (coordinatoclathrate) and those without any coordinative host-guest interaction but using steric lattice barriers provided by the host molecule (true clathrate).12 In contrast with 1c, compound 1d includes apart from the acceptor molecule 1,4dioxane the C-H donor molecule acetonitrile as an additional guest species, leading to a balanced situation with reference to the hydrogen bonding potential of the crystal components. It is safe to assume this advantage as the motivation to form the mixed guest inclusion crystal. On the other hand, the successful structure of the host compound 1 in a solvent-free state proves documentary evidence that the design strategy underlying the present host compound is not subject to a strict regularity. Although there is no possibility of exercising full hydrogen bond capacity between the host hydroxy groups, the packing occurs by the use of weaker O-H 3 3 3 π interactions19 between neighboring host molecules and the large degree of weak arene 3 3 3 arene contacts, apparently giving rise to sufficient stability of the crystal lattice. A similar behavior has previously been found with 9-phenyl-9-fluorenol, which is another case of a versatile host compound.17a Nevertheless, reflecting the specific interactions in the present compound system, the solvent inclusions are certainly better off, suggesting increased stability of their crystals. However, considering the packing coefficients (i.e., the ratio of the space occupied by a molecule to the space allotted in the unit cell)23 of the different structures as another potential measure of the crystal stability, the graduation is as follows: 1a (0.66), 1b (0.67), 1c (0.68), 1d (0.68), 1 (0.68). These ratios are within the 0.65-0.77 interval characteristic for normal closepacked organic crystals24 but range at the lower end of the

Figure 11. Packing structure of the inclusion compound 1d viewed down the c-axis. All but the host hydrogens involved in hydrogen bond formation (broken lines) are omitted for clarity.

interval. Surprisingly, the packing coefficients of the apohost and its inclusion compounds do not significantly differ. This shows that the plain and clathrate crystallization of host compounds are subject to a complex interplay of factors including closed packing and interactive group parameters and could also be influenced by the kinetics. Accordingly, a clathrate host, even when classed using the term “versatile host compound”,9 dependent on certain conditions may find a way to crystallize from an unsuitable solvent, such as chlorocyclohexane, using as an alternative less directional weaker contacts than those intended for a specific host-guest interaction.17 Put another way, the presence of functional groups suitable for a particular hydrogen bond interaction does not guarantee that such an interaction will occur unless the packing density of the crystal is acceptable. Hence, the socalled “coordinato-clathrate strategy”,15 on which the present host compound is based, should not be regarded as a strict rule with reference to the formation of inclusion crystals but a helpful framework in the search for new efficient crystal hosts. The same thing is probably true with other known design strategies of clathrate hosts which have been put to good use.13 Experimental Section Materials. The host compound 1 was prepared as described in the literature.16a The solvents were dried prior to use. Single crystals of 1 suitable for X-ray diffraction study were grown by slow evaporation of a solution in chlorocyclohexane. Single crystals of 1a-1c were obtained from solutions of 1 in the respective solvents, and 1d was obtained from a 1:1 solvent mixture. X-ray-Crystallography. The intensity data were collected on a Kappa APEX II diffractometer (Bruker-AXS) with graphite monochromated MoKa radiation (λ = 0.71073 A˚) using Φ and ω scans. Reflections were corrected for background, Lorentz and polarization effects. Preliminary structure models were derived by application of direct methods25 and were refined by full-matrix leastsquares calculation based on F2 values for all unique reflections.26 Empirical absorption correction based on multiscans was applied by using the SADABS program.27 All non-hydrogen atoms were refined anisotropically. All hydrogen atoms were included in the models in calculated positions and were refined as constrained to bonding atoms.

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Table 1. Crystallographic and Structure Refinement Data of the Compounds Studied compound

1

a

1c

1d

514.59 monoclinic P21/c 8.8018(9) 27.145(3) 22.475(2) 90.0 97.818(7) 90.0 5319.9(9) 8 2160 1.285 0.078

2 C38H26O2 3 3 C4H8O 1293.49 triclinic P1 9.7061(3) 10.8625(3) 33.3784(9) 97.918(2) 92.024(2) 103.448(2) 3381.75(17) 2 1368 1.270 0.082

C38H26O2 3 C4H8O2 3 C2H3N 643.75 monoclinic P21/c 17.7236(3) 22.5649(4) 8.4558(1) 90.0 103.210(1) 90.0 3292.25(9) 4 1360 1.299 0.082

93(2) 49074 1.2-25.1 -10/6, -32/32, -26/26 9484 0.1267

298(2) 47165 1.6-28.7 -14/12, -33/33, -17/17 8854 0.0400

153(2) 42448 1.5-27.4 -18/18, -16/14, -27/26 8861 0.0526

123(2) 61020 0.6-27.4 -12/12, -13/14, -43/43 15371 0.0323

123(2) 65133 1.2-29.2 -24/24, -30/30, -11/11 8929 0.0310

[σ2(Fo2) þ (0.0656P)2 þ 0.5090P)]-1 725 4664

[σ2(Fo2) þ (0.0927P)2 þ 0.1508P)]-1 442 5484

[σ2(Fo2) þ (0.0716P)2 þ 0.5940P)]-1 982 6518

[σ2(Fo2) þ (0.0705P)2 þ 1.4964P)]-1 887 11055

[σ2(Fo2) þ (0.0698P)2 þ 0.9191P)]-1 445 7295

0.0423 0.1403 0.897 0.22/-0.27

0.0529 0.1699 1.051 0.42/-0.37

0.0472 0.1321 1.003 0.35/-0.28

0.0485 0.1413 1.002 0.40/-0.27

0.0411 0.1290 1.071 0.34/-0.26

formula weight crystal system space group a (A˚) b (A˚) c (A˚) R (°) β (°) γ (°) V (A˚3) Z F(000) Dc (Mg m-3) μ (mm-1) data collection temperature (K) no. of collected reflections within the θ-limit (°) index ranges ( h, ( k, ( l

no. of refined parameters no. of F values used [I > 2σ(I)] final R-indices R(= Σ|ΔF|/Σ|Fo|) wR on F2 S (= goodness of fit on F2) final ΔFmax/ΔFmin (e A˚-3)

1b C38H26O2 3 2 C6H12O 714.90 monoclinic Pc 14.0610(5) 13.1034(4) 21.2401(7) 90.0 95.822(2) 90.0 3893.2(2) 4 1528 1.220 0.076

C38H26O2

no. of unique reflections Rint refinement calculations: full-matrix least- squares on all F2 values weighting expression wa

1a C38H26O2 3 C8H8O2 650.73 monoclinic P21/n 10.6055(2) 24.8966(6) 13.1568(3) 90.0 96.784(1) 90.0 3449.61(13) 4 1368 1.253 0.079

empirical formula

P = (Fo2 þ 2Fc2)/3. Table 2. Selected Conformational Parameters of the Compounds 1 and 1a-1d compound

1

1a

1b

1c

torsion angles (°) τ1 [C(14)-C(19)-C(20)-C(25)] [C(14A)-C(19A)-C(20A)-C(25A)] τ2 [O(1)-C(13)-C(14)-C(19)] [O(1A)-C(13A)-C(14A)-C(19A)] τ3 [C(20)-C(25)-C(26)-O(2)] [C(20A)-C(25A)-C(26A)-O(2A)]

92.8(4) -90.5(4) -29.3(4) 12.6(4) -20.2(4) 19.2(4)

-92.9(2)

91.3(5) -89.9(5) -16.6(4) 19.8(4) -33.4(4) 28.8(5)

94.9(2) 95.7(2) -25.0(2) -15.6(2) -13.5(2) -12.2(2)

16.7(2) 17.3(2)

1d 93.6(1) -23.9(2) -19.7(1)

Table 3. Distances (A˚) and Angles (deg) of Possible Hydrogen Bond Type Interactions of the Compounds Studied D-H 3 3 3 A 1 O(2)-H(2) 3 3 3 (O1) O(2A)-H(2A) 3 3 3 O(1A) O(1A)-H(1A) 3 3 3 C(23A)a O(1)-H(1) 3 3 3 centroid(ring D)b C(5)-H(5) 3 3 3 centroid(ring D0 )b C(10)-H(10) 3 3 3 C(15A)a C(17)-H(17) 3 3 3 centroid(ring A0 )b C(29)-H(29) 3 3 3 C(22)a C(30)-H(30) 3 3 3 C(17A)a C(16A)-H(16A) 3 3 3 C(35)a C(17A)-H(17A) 3 3 3 centroid(ring F)b C(23A)-H(23A) 3 3 3 C(35A)a C(30A)-H(30A) 3 3 3 centroid(ring C)b C(31A)-H(31A) 3 3 3 C(15)a C(34A)-H(34A) 3 3 3 C(35)a C(37A)-H(37A) 3 3 3 C(22A)a 1a O(2)-H(2) 3 3 3 O(1)

symmetry operator

D-H

D3 3 3A

H3 3 3A

D-H 3 3 3 A

x, y, z x, y, z -x, 1 - y, 1 - z x, y, z -x, 0.5 þ y, 0.5 - z x, y, z 1 þ x, y, z -1 þ x, y, z x, 1.5 - y, 0.5 þ z -1 þ x, 1.5 - y, -0.5 þ z -1 þ x, 1.5 - y, -0.5 þ z -1 þ x, y, z 1 - x, -0.5 þ y, 0.5 - z 1 - x, -0.5 þ y, 0.5 - z 1 - x, 1 - y, 1 - z -x, 1 - y, 1 - z

0.84 0.84 0.84 0.84 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95

2.837(3) 2.757(3) 3.178(3) 3.608(4) 3.619(4) 3.833(3) 3.738(4) 3.649(3) 3.641(4) 3.432(3) 3.589(4) 3.509(3) 3.649(4) 3.399(3) 3.587(3) 3.693(3)

2.05 1.98 2.34 2.99 2.76 2.89 2.97 2.72 2.78 2.80 2.87 2.80 2.90 2.69 2.76 2.88

156.6 154.0 172.5 131.2 150.2 172.8 138.5 167.4 151.1 124.2 133.1 132.2 136.2 131.4 145.5 144.9

x, y, z

0.82

2.716(1)

1.94

158.6

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D-H 3 3 3 A C(2G)-H(2G) 3 3 3 O(2) C(4G)-H(4G) 3 3 3 C(7)a C(6G)-H(6G) 3 3 3 C(35)a O(1)-H(1) 3 3 3 O(2G) C(28)-H(28) 3 3 3 O(2G) C(29)-H(29) 3 3 3 centroid(ring G)c C(35)-H(35) 3 3 3 centroid(ring D)b C(22)-H(22) 3 3 3 C(29)a C(15)-H(15) 3 3 3 C(4G)a 1b O(1)-H(1) 3 3 3 O(2) O(2)-H(2) 3 3 3 O(1F) O(1A)-H(1°) 3 3 3 O(1G) O(2A)-H(2A1) 3 3 3 O(1A) O(1F)-H(1F) 3 3 3 O(1H) O(1H)-H(1H) 3 3 3 (O2A) O(1G)-H(1G) 3 3 3 O(1I) C(1I)-H(1I1) 3 3 3 O(1) C(3I)-H(3I2) 3 3 3 O(1) C(30)-H(30) 3 3 3 centroid(ring F0 )b C(30A)-H(30A) 3 3 3 centroid(ring F)b 1c O(2)-H(2) 3 3 3 O(1) O(1)-H(1) 3 3 3 O(1F) O(2A)-H(2A1) 3 3 3 O(1A) O(1A)-H(1A) 3 3 3 O(1G) C(16)-H(16) 3 3 3 O(2F) C(8)-H(8) 3 3 3 O(2G) C(37A)-H(37A) 3 3 3 O(1G) C(18A)-H(18A) 3 3 3 O(1H) C(22A)-H(22A) 3 3 3 O(2H) C(30A)-H(30A) 3 3 3 O(2H) C(3)-H(3) 3 3 3 centroid(ring B0 )b C(4)-H(4) 3 3 3 centroid(ring F0 )b C(9)-H(9) 3 3 3 C(16)a C(34)-H(34) 3 3 3 centroid(ring C)b C(4A)-H(4A) 3 3 3 centroid(ring F)b C(23A)-H(23A) 3 3 3 centroid(ring E0 )b 1d O(2)-H(2) 3 3 3 O(1) O(1)-H(1) 3 3 3 O(1G) C(34)-H(34) 3 3 3 O(2G) C(4G)-H(4G2) 3 3 3 O(2G) C(2H)-H(2H2) 3 3 3 O(2) C(2H)-H(2H1) 3 3 3 N(1H) C(5)-H(5) 3 3 3 N(1H) C(16)-H(16) 3 3 3 centroid(ring A)b C(1G)-H(1G2) 3 3 3 centroid(ring B)b C(30)-H(30) 3 3 3 centroid(ring D)b C(36)-H(36) 3 3 3 centroid(ring D)b

Skobridis et al.

Table 3. Continued symmetry operator D-H 0.5 þ x, 0.5 - y, 0.5 þ z 0.5 - x, 0.5 þ y, 0.5 - z x, y, z -1 þ x, y, z -1 þ x, y, z -1 þ x, y, z 0.5 þ x, 0.5 - y, -0.5 þ z 0.5 þ x, 0.5 - y, 0.5 þ z 0.5 - x, -0.5 þ y, 0.5 - z

0.93 0.93 0.93 0.82 0.93 0.93 0.93 0.93 0.93

D3 3 3A 3.313(2) 3.788(2) 3.641(2) 2.793(2) 3.449(2) 3.712(2) 3.674(2) 3.690(2) 3.608(2)

H3 3 3A 2.40 2.86 2.74 2.01 2.68 2.84 2.83 2.84 2.79

D-H 3 3 3 A 166.2 174.3 163.6 159.4 139.6 156.7 151.4 153.4 147.3

x, y, z x, y, z x, y, z x, y, z x, y, z x, y, z x, y, z 1 þ x, 1 - y, 0.5 þ z 1 þ x, 1 - y, 0.5 þ z x, 2 - y, -0.5 þ z x, 1 - y, 0.5 þ z

0.84 0.84 0.84 0.84 0.84 0.84 0.84 1.00 0.99 0.95 0.95

2.720(4) 2.646(3) 2.776(3) 2.680(3) 2.676(4) 2.748(4) 2.900(4) 3.459(5) 3.367(6) 3.581(5) 3.507(5)

1.94 1.81 2.00 1.89 1.92 1.91 2.12 2.64 2.53 2.70 2.61

155.1 174.4 153.9 155.8 149.8 176.7 154.4 139.3 141.6 155.5 157.8

x, y, z x, y, z x, y, z 1 þ x, y, z 1 þ x, 1 þ y, z x, 1 þ y, z 1 þ x, y, z x, y, z 1 - x, 1 - y, -z -x, -y, -z x, y, z x, 1 þ y, z -1 þ x, y, z x, -1 þ y, -z x, y, z 1 - x, -y, -z

0.84 0.84 0.84 0.84 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95

2.661(2) 2.628(2) 2.729(2) 2.678(2) 3.370(2) 3.338(2) 3.523(2) 3.464(2) 3.590(3) 3.610(2) 3.842(3) 3.593(3) 3.370(3) 3.559(3) 3.480(3) 3.553(3)

1.86 1.79 1.93 1.84 2.44 2.43 2.76 2.53 2.74 2.74 2.93 2.66 2.68 2.94 2.58 2.70

159.1 178.9 159.6 175.4 165.9 159.8 137.6 168.1 149.4 151.8 161.4 169.0 160.5 123.9 158.4 150.3

x, y, z x, y, 1 þ z 1 - x, -0.5 þ y, 1.5 - z x, 1.5 - y, -0.5 þ z x, 0.5 - y, -0.5 þ z x, 0.5 - y, 0.5 þ z -x, 1 - y, 1 - z -x, 1 - y, 1 - z x, y, -1 þ z x, 0.5 - y, 0.5 þ z 1 - x, 1 - y, 2 - z

0.84 0.84 0.95 0.99 0.98 0.98 0.95 0.95 0.95 0.95 0.95

2.770(1) 2.757(1) 3.565(2) 3.316(2) 3.374(2) 3.434(2) 3.582(2) 3.763(2) 3.596(2) 3.521(2) 3.797(2)

1.96 1.93 2.69 2.62 2.50 2.55 2.66 2.87 2.88 2.80 2.86

160.9 166.7 154.1 127.2 148.1 149.8 163.4 156.8 130.3 133.8 170.8

a To achieve reasonable hydrogen bond geometries, an individual carbon atom instead the ring center was chosen as acceptor site. b Means center of the aromatic ring A: C(1) 3 3 3 C(6), B: C(7) 3 3 3 C(12), C: C(14) 3 3 3 C(19), D: C(20) 3 3 3 C(25), E: C(27) 3 3 3 C(32), F: C(33) 3 3 3 C(38), A0 : C(1A) 3 3 3 C(6A), B0 : C(7A) 3 3 3 C(12A), C0 : C(14A) 3 3 3 C(19A), D0 : C(20A) 3 3 3 C(25A), E0 : C(27A) 3 3 3 C(32A), F0 : C(33A) 3 3 3 C(38A). c Means center of the aromatic ring given by C(1G) 3 3 3 C(6G) of phenyl acetate.

Acknowledgment. K.S. thanks the State Scholarships Foundation (IKY) for supporting this work. (4)

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