Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106033117/ga3021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106033117/ga3021Isup2.hkl |
CCDC reference: 625690
C6-Pyridone was synthesized as previously reported by Robinson et al. (2005). Dilute solutions (5 mM) of C6-pyridone and NBA in propan-2-ol were mixed in equal volume and allowed to stand at room temperature until solvent evaporation produced colourless crystals of (I). NMR and FT–IR data are available in the archived CIF.
The rotational orientation of the methyl group was refined by the circular Fourier method available in SHELXL97 (Sheldrick, 1997). The position of the hydroxyl H atom was determined in a similar manner. All H atoms were treated as riding, with C—H = 0.99 Å and O—H = 0.84 Å, and with Uiso(H) = 1.5Ueq(parent) for hydroxyl and methyl H atoms, or 1.2Ueq(parent) for all other H atoms.
Our interest in the pyridin-4(1H)-one moiety (hereinafter 4-pyridone) stems from its potential for incorporation into liquid crystal units (Dyer et al., 1997), due to its inherent large birefringence and polarizability (Dirk et al., 1986). Such liquid crystals have the potential to be integrated into electro-optic devices, including a number of different flat-panel display configurations (Kuo & Suzuki, 2002). In fact, the 1-phenylpyridin-4(1H)-one aromatic core is reminiscent of the counterpart in the classical nCB and nOCB liquid crystals (Davey et al., 2005). Furthermore, the C═O group of 4-pyridone could be a better hydrogen-bond acceptor compared with the nitrile group of nCB and nOCB (Chen & Dannenberg, 2006). Thus, the 4-pyridone moiety may prove useful as a robust hydrogen-bond unit in creating thin organic films with a macroscopic noncentrosymmetric architecture (Dyer et al., 2003; Facchetti, Annoni et al., 2004; Facchetti, Letizia et al., 2004). We have demonstrated previously that molecules containing the 4-pyridone moiety can crystallize either as a neat crystal (Li et al., 2005) or as a monohydrate (Robinson et al., 2005). This report details the structure of the hydrogen-bonded heterodimer, (I), of 1-(4-(hexyloxy)phenyl)pyridin-4(1H)-one (hereinafter C6-pyridone) with 4-nitrile benzoic acid (hereinafter NBA), which represents the first evidence of robust hydrogen-bond formation between the 4-pyridone moiety and the benzoic acid moiety.
As can be seen in Fig. 1, the asymmetric heterodimer, (I), is made up of molecules of C6-pyridone and NBA in a 1:1 ratio. The dihedral angle between the 4-pyridone and the phenyl ring of the C6-pyridone molecule is 40.61 (8)°, as opposed to the value of 46.19 (19)° found for C6-pyridone monohydrate (Robinson et al., 2005). The torsion angle C14—C15—C16—C17 of 62.7 (2)° shows that the terminal methyl group of the alkoxy chain is twisted significantly out of the `all trans' conformation (Hori & Wu, 1999). Atom O2 is essentially in the 4-pyridone plane, its deviation being only 0.057 (1) Å. Atoms C25 and N2 (C≡N group) are out of the NBA phenyl ring by only 0.041 (2) and 0.095 (2) Å, respectively. The carboxyl group (O4/C18/O3) forms a dihedral angle of 9.2 (1)° with the NBA phenyl ring plane, compared with the equivalent angle of 7.7 (7)° in the NBA homodimer [Higashi & Osaki, 1981; Cambridge Structural Database refcode TAGNAR (November 2005 release; Allen, 2002)]. While bond distances and angles are generally unremarkable, the C1═O2 double bond length of 1.268 (2) Å is slightly longer than the value of 1.247 (2) Å in 1-(4-decyl-phenyl)-1H-pyridin-4-one (Li et al., 2005), a possible consequence of the stronger hydrogen-bond interaction effect in the heterodimer.
The two molecular components of (I) are linked end-to-end via O3—H3···O2 and C2—H2···O4 hydrogen-bond interactions, graph set R22(8) (Bernstein et al., 1995), as shown in Figs. 1 and 2. Noticeably, O3—H3···O2 is a homonuclear hydrogen bond (Table 1), which can be classified as a strong hydrogen-bond interaction (Gilli et al., 1994), while the C—H···O bond is rather weak, even for a non-traditional interaction. Considering the 14.8 (3)° dihedral angle between O2/C1/C2 and O4/C18/O3, the R22(8) ring is not planar. Nevertheless, the hydrogen-bond interactions seem robust enough to make the ring rigid and induce liquid crystallinity (Collings & Hird, 1997). Thus, the 4-pyridone moiety may prove to be a useful building block in self-assembled materials and liquid crystals.
The dimers are linked in a side-by-side fashion by three additional C—H···O interactions (Table 1, Fig. 2), which produces graph-set motifs R23(7) and R23(13). The result is a wide infinite molecular ribbon, which propagates in the [010] direction (vertically in Fig. 2) within the (201) plane. The ribbon is roughly 29 Å wide, and the edges of the ribbon (on the left and right of Fig. 2) are composed of terminal methyl groups of the alkoxy `tail'. The dimers shown in Fig. 2 are essentially in the plane of the paper and the ribbon repeats every other link and has only a minor zigzag character. It should be noted that the ribbon is held together entirely by non-traditional hydrogen bonds and is thus quite loosely knit. Full details of the hydrogen-bond geometry are given in Table 1.
The ribbons are interconnected via π–π stacking and C—H···π(arene) interactions. Fig. 3 shows an end-on view of parallel ribbons emerging from the paper along [010]. The π-π -stacking interactions are between Cg1 and Cg2, where Cg1 is the centroid of the origin 4-pyridone ring and Cg2 is the centroid of the NBA phenyl ring at (1 - x, 1 - y, 1 - z). The centroid-to-centroid distance is 3.6891 (10) Å, the dihedral angle is 7.90 (8)° and the perpendicular distance is 3.515 Å, with a 1.05 Å offset, and this geometry is in good agreement with similar interactions (Wheatley et al., 1999). In addition, C—H···π(arene) interactions interconnect the parallel ribbons (entry 6 in Table 1, not shown in Fig. 3). This interaction is in reasonably good agreement with the most frequently observed values (Braga et al., 1998).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT and SADABS (Bruker, 2005); program(s) used to solve structure: SIR92 (Burla et al., 1989); program(s) used to refine structure: LS in TEXSAN (Molecular Structure Corporation, 1997) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and SHELXTL (Bruker, 2005); software used to prepare material for publication: SHELXL97 and PLATON.
C17H21NO2·C8H5NO2 | F(000) = 888 |
Mr = 418.48 | Dx = 1.285 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9833 reflections |
a = 14.4115 (6) Å | θ = 2.4–26.4° |
b = 11.4432 (4) Å | µ = 0.09 mm−1 |
c = 13.4320 (5) Å | T = 100 K |
β = 102.434 (2)° | Block-like, colorless |
V = 2163.16 (14) Å3 | 0.30 × 0.22 × 0.16 mm |
Z = 4 |
Bruker Kappa APEXII CCD area-detector diffractometer | 4460 independent reflections |
Radiation source: X-ray tube | 3365 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.077 |
φ and ω scans | θmax = 26.5°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −18→18 |
Tmin = 0.773, Tmax = 0.986 | k = −14→14 |
53973 measured reflections | l = −16→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0598P)2 + 0.5135P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
4460 reflections | Δρmax = 0.26 e Å−3 |
283 parameters | Δρmin = −0.29 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0027 (6) |
C17H21NO2·C8H5NO2 | V = 2163.16 (14) Å3 |
Mr = 418.48 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.4115 (6) Å | µ = 0.09 mm−1 |
b = 11.4432 (4) Å | T = 100 K |
c = 13.4320 (5) Å | 0.30 × 0.22 × 0.16 mm |
β = 102.434 (2)° |
Bruker Kappa APEXII CCD area-detector diffractometer | 4460 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 3365 reflections with I > 2σ(I) |
Tmin = 0.773, Tmax = 0.986 | Rint = 0.077 |
53973 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.26 e Å−3 |
4460 reflections | Δρmin = −0.29 e Å−3 |
283 parameters |
Experimental. 1H-NMR (300 MHz, DMSO) δ 8.09 (d, J = 9.1 Hz, 2H), 7.98 (d, J = 9.1 Hz, 2H), 7.89 (d, J = 7.5 Hz, 2H), 7.45 (d, J = 9.0 Hz, 2H), 7.06 (d, J = 9.0 Hz, 2H), 6.20 (d, J = 7.5 Hz, 2H), 4.01 (t, J = 6.6 Hz, 2H), 1.72 (m, 2H), 1.33–1.31 (m, 6H), 0.88 (t, J = 6.6 Hz, 3H); 13C-NMR (75 MHz, DMSO) δ 177.9 (C=O), 166.8 (COOH), 158.8, 140.9, 136.7, 135.6, 133.4, 130.6, 124.8, 118.9, 118.4, 116.1, 115.8, 68.6, 31.7, 29.3, 25.9, 22.8, 14.6. F T—IR (KBr, cm-1) 1691, 1677, 1665, 1628, 1607, 1501, 1467. |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.78847 (9) | 0.26899 (10) | 1.27242 (9) | 0.0198 (3) | |
O2 | 0.42137 (9) | 0.55754 (10) | 0.63528 (9) | 0.0214 (3) | |
O3 | 0.36128 (9) | 0.47288 (10) | 0.45967 (9) | 0.0231 (3) | |
H3 | 0.3867 | 0.4842 | 0.5213 | 0.035* | |
O4 | 0.41806 (9) | 0.29167 (10) | 0.49454 (9) | 0.0228 (3) | |
N1 | 0.59803 (10) | 0.44438 (12) | 0.89741 (10) | 0.0153 (3) | |
N2 | 0.14883 (12) | 0.20871 (16) | −0.04889 (13) | 0.0330 (4) | |
C1 | 0.47803 (12) | 0.52251 (14) | 0.71540 (13) | 0.0164 (4) | |
C2 | 0.53097 (12) | 0.41614 (14) | 0.72134 (13) | 0.0170 (4) | |
H2 | 0.5259 | 0.3693 | 0.6620 | 0.020* | |
C3 | 0.58791 (12) | 0.38094 (14) | 0.80941 (13) | 0.0166 (4) | |
H3A | 0.6221 | 0.3098 | 0.8104 | 0.020* | |
C4 | 0.55015 (12) | 0.54816 (14) | 0.89433 (13) | 0.0171 (4) | |
H4 | 0.5575 | 0.5936 | 0.9547 | 0.021* | |
C5 | 0.49304 (13) | 0.58744 (14) | 0.80811 (13) | 0.0184 (4) | |
H5 | 0.4619 | 0.6604 | 0.8090 | 0.022* | |
C6 | 0.65233 (12) | 0.40105 (14) | 0.99267 (13) | 0.0157 (4) | |
C7 | 0.64668 (12) | 0.28313 (14) | 1.01624 (13) | 0.0167 (4) | |
H7 | 0.6096 | 0.2312 | 0.9685 | 0.020* | |
C8 | 0.69520 (12) | 0.24247 (15) | 1.10915 (13) | 0.0173 (4) | |
H8 | 0.6932 | 0.1616 | 1.1244 | 0.021* | |
C9 | 0.74727 (12) | 0.31799 (14) | 1.18134 (13) | 0.0165 (4) | |
C10 | 0.75397 (12) | 0.43574 (14) | 1.15666 (13) | 0.0186 (4) | |
H10 | 0.7905 | 0.4879 | 1.2046 | 0.022* | |
C11 | 0.70714 (12) | 0.47612 (14) | 1.06199 (13) | 0.0182 (4) | |
H11 | 0.7127 | 0.5559 | 1.0445 | 0.022* | |
C12 | 0.83844 (13) | 0.34508 (15) | 1.35125 (13) | 0.0216 (4) | |
H12A | 0.7941 | 0.4036 | 1.3691 | 0.026* | |
H12B | 0.8894 | 0.3871 | 1.3270 | 0.026* | |
C13 | 0.88061 (13) | 0.27279 (15) | 1.44329 (13) | 0.0201 (4) | |
H13A | 0.9273 | 0.2172 | 1.4258 | 0.024* | |
H13B | 0.8298 | 0.2271 | 1.4644 | 0.024* | |
C14 | 0.92947 (13) | 0.35037 (15) | 1.53098 (13) | 0.0212 (4) | |
H14A | 0.8822 | 0.4053 | 1.5482 | 0.025* | |
H14B | 0.9791 | 0.3972 | 1.5086 | 0.025* | |
C15 | 0.97504 (13) | 0.28175 (15) | 1.62619 (13) | 0.0202 (4) | |
H15A | 1.0159 | 0.2199 | 1.6069 | 0.024* | |
H15B | 0.9243 | 0.2430 | 1.6534 | 0.024* | |
C16 | 1.03466 (13) | 0.35659 (16) | 1.71004 (14) | 0.0239 (4) | |
H16A | 1.0654 | 0.3051 | 1.7668 | 0.029* | |
H16B | 1.0856 | 0.3951 | 1.6829 | 0.029* | |
C17 | 0.97755 (14) | 0.44982 (17) | 1.75139 (15) | 0.0281 (5) | |
H17A | 0.9549 | 0.5082 | 1.6983 | 0.042* | |
H17B | 1.0179 | 0.4878 | 1.8105 | 0.042* | |
H17C | 0.9230 | 0.4134 | 1.7719 | 0.042* | |
C18 | 0.37320 (12) | 0.36264 (14) | 0.43596 (13) | 0.0180 (4) | |
C19 | 0.32482 (12) | 0.33306 (14) | 0.32950 (13) | 0.0167 (4) | |
C20 | 0.34235 (12) | 0.22445 (14) | 0.29059 (14) | 0.0186 (4) | |
H20 | 0.3848 | 0.1715 | 0.3319 | 0.022* | |
C21 | 0.29854 (13) | 0.19297 (15) | 0.19244 (14) | 0.0212 (4) | |
H21 | 0.3109 | 0.1188 | 0.1662 | 0.025* | |
C22 | 0.23637 (12) | 0.27047 (15) | 0.13243 (13) | 0.0187 (4) | |
C23 | 0.21814 (13) | 0.37975 (15) | 0.17067 (14) | 0.0213 (4) | |
H23 | 0.1755 | 0.4326 | 0.1295 | 0.026* | |
C24 | 0.26244 (12) | 0.40992 (15) | 0.26823 (13) | 0.0198 (4) | |
H24 | 0.2504 | 0.4842 | 0.2943 | 0.024* | |
C25 | 0.18831 (13) | 0.23658 (16) | 0.03127 (15) | 0.0228 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0267 (7) | 0.0127 (6) | 0.0174 (7) | −0.0011 (5) | −0.0010 (5) | 0.0006 (5) |
O2 | 0.0315 (7) | 0.0106 (6) | 0.0192 (7) | 0.0019 (5) | −0.0007 (6) | 0.0009 (5) |
O3 | 0.0384 (8) | 0.0089 (6) | 0.0190 (7) | 0.0028 (5) | −0.0008 (6) | −0.0006 (5) |
O4 | 0.0311 (7) | 0.0118 (6) | 0.0235 (7) | 0.0027 (5) | 0.0014 (6) | 0.0037 (5) |
N1 | 0.0204 (8) | 0.0071 (7) | 0.0180 (8) | 0.0000 (6) | 0.0030 (6) | 0.0000 (6) |
N2 | 0.0338 (10) | 0.0377 (10) | 0.0268 (10) | 0.0023 (8) | 0.0050 (8) | −0.0061 (8) |
C1 | 0.0222 (9) | 0.0091 (8) | 0.0178 (9) | −0.0030 (7) | 0.0041 (7) | 0.0019 (7) |
C2 | 0.0229 (10) | 0.0093 (8) | 0.0186 (9) | −0.0005 (7) | 0.0039 (8) | −0.0028 (7) |
C3 | 0.0219 (9) | 0.0080 (8) | 0.0197 (9) | 0.0007 (7) | 0.0044 (8) | −0.0023 (7) |
C4 | 0.0242 (10) | 0.0062 (8) | 0.0214 (9) | 0.0001 (7) | 0.0059 (8) | −0.0020 (7) |
C5 | 0.0265 (10) | 0.0074 (8) | 0.0214 (9) | 0.0011 (7) | 0.0055 (8) | 0.0002 (7) |
C6 | 0.0192 (9) | 0.0118 (8) | 0.0156 (9) | 0.0015 (7) | 0.0028 (7) | −0.0002 (7) |
C7 | 0.0207 (9) | 0.0097 (8) | 0.0196 (9) | −0.0009 (7) | 0.0042 (7) | −0.0040 (7) |
C8 | 0.0210 (9) | 0.0076 (8) | 0.0235 (10) | 0.0007 (7) | 0.0053 (8) | −0.0001 (7) |
C9 | 0.0186 (9) | 0.0133 (8) | 0.0170 (9) | 0.0019 (7) | 0.0027 (7) | 0.0012 (7) |
C10 | 0.0233 (10) | 0.0110 (8) | 0.0201 (9) | −0.0028 (7) | 0.0017 (8) | −0.0035 (7) |
C11 | 0.0242 (10) | 0.0082 (8) | 0.0217 (10) | −0.0021 (7) | 0.0039 (8) | 0.0002 (7) |
C12 | 0.0282 (10) | 0.0139 (9) | 0.0199 (10) | −0.0028 (8) | −0.0008 (8) | −0.0019 (7) |
C13 | 0.0241 (10) | 0.0150 (9) | 0.0205 (10) | −0.0005 (7) | 0.0036 (8) | 0.0013 (7) |
C14 | 0.0265 (10) | 0.0148 (9) | 0.0203 (10) | 0.0000 (7) | 0.0008 (8) | 0.0018 (7) |
C15 | 0.0224 (10) | 0.0162 (9) | 0.0215 (10) | 0.0001 (7) | 0.0038 (8) | 0.0010 (7) |
C16 | 0.0265 (10) | 0.0207 (9) | 0.0220 (10) | 0.0001 (8) | −0.0002 (8) | 0.0003 (8) |
C17 | 0.0337 (12) | 0.0248 (10) | 0.0251 (10) | −0.0013 (9) | 0.0045 (9) | −0.0032 (8) |
C18 | 0.0222 (10) | 0.0102 (8) | 0.0227 (10) | −0.0009 (7) | 0.0073 (8) | 0.0029 (7) |
C19 | 0.0208 (9) | 0.0098 (8) | 0.0208 (9) | −0.0016 (7) | 0.0071 (8) | 0.0015 (7) |
C20 | 0.0232 (10) | 0.0094 (8) | 0.0239 (10) | 0.0011 (7) | 0.0069 (8) | 0.0030 (7) |
C21 | 0.0275 (10) | 0.0117 (8) | 0.0255 (10) | −0.0009 (7) | 0.0085 (8) | −0.0024 (7) |
C22 | 0.0214 (9) | 0.0160 (9) | 0.0197 (9) | −0.0028 (7) | 0.0064 (8) | −0.0004 (7) |
C23 | 0.0231 (10) | 0.0146 (9) | 0.0254 (10) | 0.0011 (7) | 0.0035 (8) | 0.0026 (7) |
C24 | 0.0254 (10) | 0.0089 (8) | 0.0249 (10) | −0.0001 (7) | 0.0049 (8) | −0.0008 (7) |
C25 | 0.0245 (10) | 0.0189 (9) | 0.0257 (11) | 0.0017 (8) | 0.0069 (9) | −0.0005 (8) |
O1—C9 | 1.360 (2) | C12—H12A | 0.9900 |
O1—C12 | 1.439 (2) | C12—H12B | 0.9900 |
O2—C1 | 1.268 (2) | C13—C14 | 1.521 (2) |
O3—C18 | 1.321 (2) | C13—H13A | 0.9900 |
O3—H3 | 0.8400 | C13—H13B | 0.9900 |
O4—C18 | 1.216 (2) | C14—C15 | 1.524 (2) |
N1—C3 | 1.368 (2) | C14—H14A | 0.9900 |
N1—C4 | 1.370 (2) | C14—H14B | 0.9900 |
N1—C6 | 1.437 (2) | C15—C16 | 1.524 (2) |
N2—C25 | 1.149 (2) | C15—H15A | 0.9900 |
C1—C5 | 1.426 (2) | C15—H15B | 0.9900 |
C1—C2 | 1.430 (2) | C16—C17 | 1.523 (3) |
C2—C3 | 1.348 (2) | C16—H16A | 0.9900 |
C2—H2 | 0.9500 | C16—H16B | 0.9900 |
C3—H3A | 0.9500 | C17—H17A | 0.9800 |
C4—C5 | 1.345 (2) | C17—H17B | 0.9800 |
C4—H4 | 0.9500 | C17—H17C | 0.9800 |
C5—H5 | 0.9500 | C18—C19 | 1.489 (3) |
C6—C11 | 1.383 (2) | C19—C20 | 1.392 (2) |
C6—C7 | 1.392 (2) | C19—C24 | 1.393 (2) |
C7—C8 | 1.374 (2) | C20—C21 | 1.381 (2) |
C7—H7 | 0.9500 | C20—H20 | 0.9500 |
C8—C9 | 1.392 (2) | C21—C22 | 1.388 (2) |
C8—H8 | 0.9500 | C21—H21 | 0.9500 |
C9—C10 | 1.396 (2) | C22—C23 | 1.398 (2) |
C10—C11 | 1.384 (2) | C22—C25 | 1.439 (3) |
C10—H10 | 0.9500 | C23—C24 | 1.372 (2) |
C11—H11 | 0.9500 | C23—H23 | 0.9500 |
C12—C13 | 1.503 (2) | C24—H24 | 0.9500 |
C9—O1—C12 | 117.70 (13) | C14—C13—H13B | 109.5 |
C18—O3—H3 | 109.5 | H13A—C13—H13B | 108.1 |
C3—N1—C4 | 118.34 (14) | C13—C14—C15 | 113.15 (14) |
C3—N1—C6 | 121.51 (14) | C13—C14—H14A | 108.9 |
C4—N1—C6 | 120.03 (14) | C15—C14—H14A | 108.9 |
O2—C1—C5 | 121.70 (15) | C13—C14—H14B | 108.9 |
O2—C1—C2 | 123.72 (15) | C15—C14—H14B | 108.9 |
C5—C1—C2 | 114.58 (15) | H14A—C14—H14B | 107.8 |
C3—C2—C1 | 121.34 (15) | C14—C15—C16 | 113.77 (15) |
C3—C2—H2 | 119.3 | C14—C15—H15A | 108.8 |
C1—C2—H2 | 119.3 | C16—C15—H15A | 108.8 |
C2—C3—N1 | 122.09 (15) | C14—C15—H15B | 108.8 |
C2—C3—H3A | 119.0 | C16—C15—H15B | 108.8 |
N1—C3—H3A | 119.0 | H15A—C15—H15B | 107.7 |
C5—C4—N1 | 121.77 (15) | C17—C16—C15 | 113.57 (15) |
C5—C4—H4 | 119.1 | C17—C16—H16A | 108.9 |
N1—C4—H4 | 119.1 | C15—C16—H16A | 108.9 |
C4—C5—C1 | 121.82 (16) | C17—C16—H16B | 108.9 |
C4—C5—H5 | 119.1 | C15—C16—H16B | 108.9 |
C1—C5—H5 | 119.1 | H16A—C16—H16B | 107.7 |
C11—C6—C7 | 120.13 (16) | C16—C17—H17A | 109.5 |
C11—C6—N1 | 120.53 (15) | C16—C17—H17B | 109.5 |
C7—C6—N1 | 119.31 (15) | H17A—C17—H17B | 109.5 |
C8—C7—C6 | 119.43 (16) | C16—C17—H17C | 109.5 |
C8—C7—H7 | 120.3 | H17A—C17—H17C | 109.5 |
C6—C7—H7 | 120.3 | H17B—C17—H17C | 109.5 |
C7—C8—C9 | 121.02 (16) | O4—C18—O3 | 124.09 (16) |
C7—C8—H8 | 119.5 | O4—C18—C19 | 122.93 (15) |
C9—C8—H8 | 119.5 | O3—C18—C19 | 112.97 (14) |
O1—C9—C8 | 115.85 (15) | C20—C19—C24 | 119.21 (16) |
O1—C9—C10 | 124.91 (15) | C20—C19—C18 | 118.57 (15) |
C8—C9—C10 | 119.24 (16) | C24—C19—C18 | 122.22 (15) |
C11—C10—C9 | 119.69 (16) | C21—C20—C19 | 120.56 (16) |
C11—C10—H10 | 120.2 | C21—C20—H20 | 119.7 |
C9—C10—H10 | 120.2 | C19—C20—H20 | 119.7 |
C6—C11—C10 | 120.40 (16) | C20—C21—C22 | 119.51 (16) |
C6—C11—H11 | 119.8 | C20—C21—H21 | 120.2 |
C10—C11—H11 | 119.8 | C22—C21—H21 | 120.2 |
O1—C12—C13 | 108.79 (14) | C21—C22—C23 | 120.46 (16) |
O1—C12—H12A | 109.9 | C21—C22—C25 | 119.68 (16) |
C13—C12—H12A | 109.9 | C23—C22—C25 | 119.84 (16) |
O1—C12—H12B | 109.9 | C24—C23—C22 | 119.35 (17) |
C13—C12—H12B | 109.9 | C24—C23—H23 | 120.3 |
H12A—C12—H12B | 108.3 | C22—C23—H23 | 120.3 |
C12—C13—C14 | 110.70 (14) | C23—C24—C19 | 120.91 (16) |
C12—C13—H13A | 109.5 | C23—C24—H24 | 119.5 |
C14—C13—H13A | 109.5 | C19—C24—H24 | 119.5 |
C12—C13—H13B | 109.5 | N2—C25—C22 | 178.9 (2) |
O2—C1—C2—C3 | −177.75 (16) | C7—C6—C11—C10 | −2.4 (3) |
C5—C1—C2—C3 | 1.7 (2) | N1—C6—C11—C10 | 175.36 (15) |
C1—C2—C3—N1 | 0.1 (3) | C9—C10—C11—C6 | 1.3 (3) |
C4—N1—C3—C2 | −1.6 (2) | C9—O1—C12—C13 | −178.21 (14) |
C6—N1—C3—C2 | 174.49 (16) | O1—C12—C13—C14 | −176.75 (14) |
C3—N1—C4—C5 | 1.0 (2) | C12—C13—C14—C15 | −179.12 (15) |
C6—N1—C4—C5 | −175.07 (16) | C13—C14—C15—C16 | 172.79 (15) |
N1—C4—C5—C1 | 0.9 (3) | C14—C15—C16—C17 | 62.7 (2) |
O2—C1—C5—C4 | 177.24 (16) | O4—C18—C19—C20 | −9.2 (3) |
C2—C1—C5—C4 | −2.2 (2) | O3—C18—C19—C20 | 171.44 (15) |
C3—N1—C6—C11 | 142.83 (17) | O4—C18—C19—C24 | 170.38 (17) |
C4—N1—C6—C11 | −41.2 (2) | O3—C18—C19—C24 | −9.0 (2) |
C3—N1—C6—C7 | −39.4 (2) | C24—C19—C20—C21 | 0.0 (3) |
C4—N1—C6—C7 | 136.59 (17) | C18—C19—C20—C21 | 179.57 (15) |
C11—C6—C7—C8 | 0.6 (3) | C19—C20—C21—C22 | −0.2 (3) |
N1—C6—C7—C8 | −177.14 (15) | C20—C21—C22—C23 | 0.1 (3) |
C6—C7—C8—C9 | 2.2 (3) | C20—C21—C22—C25 | −178.06 (16) |
C12—O1—C9—C8 | −176.54 (15) | C21—C22—C23—C24 | 0.1 (3) |
C12—O1—C9—C10 | 3.5 (2) | C25—C22—C23—C24 | 178.26 (16) |
C7—C8—C9—O1 | 176.83 (15) | C22—C23—C24—C19 | −0.3 (3) |
C7—C8—C9—C10 | −3.2 (3) | C20—C19—C24—C23 | 0.2 (3) |
O1—C9—C10—C11 | −178.61 (16) | C18—C19—C24—C23 | −179.35 (16) |
C8—C9—C10—C11 | 1.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.84 | 1.72 | 2.5244 (17) | 159 |
C2—H2···O4 | 0.95 | 2.60 | 3.438 (2) | 147 |
C4—H4···O4i | 0.95 | 2.37 | 3.148 (2) | 139 |
C7—H7···O2ii | 0.95 | 2.41 | 3.303 (2) | 156 |
C8—H8···O3ii | 0.95 | 2.48 | 3.273 (2) | 140 |
C13—H13B···Cg3iii | 0.99 | 2.91 | 3.856 (2) | 161 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x, −y−1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C17H21NO2·C8H5NO2 |
Mr | 418.48 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 14.4115 (6), 11.4432 (4), 13.4320 (5) |
β (°) | 102.434 (2) |
V (Å3) | 2163.16 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.30 × 0.22 × 0.16 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.773, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 53973, 4460, 3365 |
Rint | 0.077 |
(sin θ/λ)max (Å−1) | 0.627 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.123, 1.08 |
No. of reflections | 4460 |
No. of parameters | 283 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.29 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SAINT and SADABS (Bruker, 2005), SIR92 (Burla et al., 1989), LS in TEXSAN (Molecular Structure Corporation, 1997) and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and SHELXTL (Bruker, 2005), SHELXL97 and PLATON.
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.84 | 1.72 | 2.5244 (17) | 159 |
C2—H2···O4 | 0.95 | 2.60 | 3.438 (2) | 147 |
C4—H4···O4i | 0.95 | 2.37 | 3.148 (2) | 139 |
C7—H7···O2ii | 0.95 | 2.41 | 3.303 (2) | 156 |
C8—H8···O3ii | 0.95 | 2.48 | 3.273 (2) | 140 |
C13—H13B···Cg3iii | 0.99 | 2.91 | 3.856 (2) | 161 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) −x+1, y−1/2, −z+3/2; (iii) x, −y−1/2, z−1/2. |
Our interest in the pyridin-4(1H)-one moiety (hereinafter 4-pyridone) stems from its potential for incorporation into liquid crystal units (Dyer et al., 1997), due to its inherent large birefringence and polarizability (Dirk et al., 1986). Such liquid crystals have the potential to be integrated into electro-optic devices, including a number of different flat-panel display configurations (Kuo & Suzuki, 2002). In fact, the 1-phenylpyridin-4(1H)-one aromatic core is reminiscent of the counterpart in the classical nCB and nOCB liquid crystals (Davey et al., 2005). Furthermore, the C═O group of 4-pyridone could be a better hydrogen-bond acceptor compared with the nitrile group of nCB and nOCB (Chen & Dannenberg, 2006). Thus, the 4-pyridone moiety may prove useful as a robust hydrogen-bond unit in creating thin organic films with a macroscopic noncentrosymmetric architecture (Dyer et al., 2003; Facchetti, Annoni et al., 2004; Facchetti, Letizia et al., 2004). We have demonstrated previously that molecules containing the 4-pyridone moiety can crystallize either as a neat crystal (Li et al., 2005) or as a monohydrate (Robinson et al., 2005). This report details the structure of the hydrogen-bonded heterodimer, (I), of 1-(4-(hexyloxy)phenyl)pyridin-4(1H)-one (hereinafter C6-pyridone) with 4-nitrile benzoic acid (hereinafter NBA), which represents the first evidence of robust hydrogen-bond formation between the 4-pyridone moiety and the benzoic acid moiety.
As can be seen in Fig. 1, the asymmetric heterodimer, (I), is made up of molecules of C6-pyridone and NBA in a 1:1 ratio. The dihedral angle between the 4-pyridone and the phenyl ring of the C6-pyridone molecule is 40.61 (8)°, as opposed to the value of 46.19 (19)° found for C6-pyridone monohydrate (Robinson et al., 2005). The torsion angle C14—C15—C16—C17 of 62.7 (2)° shows that the terminal methyl group of the alkoxy chain is twisted significantly out of the `all trans' conformation (Hori & Wu, 1999). Atom O2 is essentially in the 4-pyridone plane, its deviation being only 0.057 (1) Å. Atoms C25 and N2 (C≡N group) are out of the NBA phenyl ring by only 0.041 (2) and 0.095 (2) Å, respectively. The carboxyl group (O4/C18/O3) forms a dihedral angle of 9.2 (1)° with the NBA phenyl ring plane, compared with the equivalent angle of 7.7 (7)° in the NBA homodimer [Higashi & Osaki, 1981; Cambridge Structural Database refcode TAGNAR (November 2005 release; Allen, 2002)]. While bond distances and angles are generally unremarkable, the C1═O2 double bond length of 1.268 (2) Å is slightly longer than the value of 1.247 (2) Å in 1-(4-decyl-phenyl)-1H-pyridin-4-one (Li et al., 2005), a possible consequence of the stronger hydrogen-bond interaction effect in the heterodimer.
The two molecular components of (I) are linked end-to-end via O3—H3···O2 and C2—H2···O4 hydrogen-bond interactions, graph set R22(8) (Bernstein et al., 1995), as shown in Figs. 1 and 2. Noticeably, O3—H3···O2 is a homonuclear hydrogen bond (Table 1), which can be classified as a strong hydrogen-bond interaction (Gilli et al., 1994), while the C—H···O bond is rather weak, even for a non-traditional interaction. Considering the 14.8 (3)° dihedral angle between O2/C1/C2 and O4/C18/O3, the R22(8) ring is not planar. Nevertheless, the hydrogen-bond interactions seem robust enough to make the ring rigid and induce liquid crystallinity (Collings & Hird, 1997). Thus, the 4-pyridone moiety may prove to be a useful building block in self-assembled materials and liquid crystals.
The dimers are linked in a side-by-side fashion by three additional C—H···O interactions (Table 1, Fig. 2), which produces graph-set motifs R23(7) and R23(13). The result is a wide infinite molecular ribbon, which propagates in the [010] direction (vertically in Fig. 2) within the (201) plane. The ribbon is roughly 29 Å wide, and the edges of the ribbon (on the left and right of Fig. 2) are composed of terminal methyl groups of the alkoxy `tail'. The dimers shown in Fig. 2 are essentially in the plane of the paper and the ribbon repeats every other link and has only a minor zigzag character. It should be noted that the ribbon is held together entirely by non-traditional hydrogen bonds and is thus quite loosely knit. Full details of the hydrogen-bond geometry are given in Table 1.
The ribbons are interconnected via π–π stacking and C—H···π(arene) interactions. Fig. 3 shows an end-on view of parallel ribbons emerging from the paper along [010]. The π-π -stacking interactions are between Cg1 and Cg2, where Cg1 is the centroid of the origin 4-pyridone ring and Cg2 is the centroid of the NBA phenyl ring at (1 - x, 1 - y, 1 - z). The centroid-to-centroid distance is 3.6891 (10) Å, the dihedral angle is 7.90 (8)° and the perpendicular distance is 3.515 Å, with a 1.05 Å offset, and this geometry is in good agreement with similar interactions (Wheatley et al., 1999). In addition, C—H···π(arene) interactions interconnect the parallel ribbons (entry 6 in Table 1, not shown in Fig. 3). This interaction is in reasonably good agreement with the most frequently observed values (Braga et al., 1998).