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The two components of the title heterodimer, C17H21NO2·C8H5NO2, are linked end-to-end via O—H...O(=C) and C—H...O(=C) hydrogen-bond inter­actions. Additional lateral C—H...O inter­actions link the dimers in a side-by-side fashion to produce wide infinite mol­ecular ribbons. Adjacent ribbons are inter­connected via π–π stacking and C—H...π(arene) inter­actions. This structure represents the first evidence of robust hydrogen-bond formation between the moieties of pyridin-4(1H)-one and benzoic acid.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106033117/ga3021sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106033117/ga3021Isup2.hkl
Contains datablock I

CCDC reference: 625690

Comment top

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 CO 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 (CN 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 C1O2 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 ππ 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).

Experimental top

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.

Refinement top

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.

Structure description top

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 CO 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 (CN 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 C1O2 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 ππ 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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure and atom-numbering scheme for (I). Displacement ellipsoids are drawn at the 70% probablilty level and H atoms are shown as small spheres of arbitrary radii. Dashed lines represent hydrogen bonds. Small black circles denote the centroids of rings involved in ππ stacking.
[Figure 2] Fig. 2. The hydrogen bonding in (I). Infinite molecular ribbons propagate along [010] as a result of O—H···O and C—H···O interactions coupled with unit translations (see Table 1). H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) 1 - x, 1/2 + y, 3/2 - z; (ii) 1 - x, y - 1/2, 3/2 - z.]
[Figure 3] Fig. 3. The packing of (I) via molecular ππ stacking interactions (dashed lines). Shown are portions of six molecular ribbons which emerge from the plane of the paper along [010].
1-[4-(hexyloxy)phenyl]pyridin-4(1H)-one–4-cyanobenzoic acid (1/1) top
Crystal data top
C17H21NO2·C8H5NO2F(000) = 888
Mr = 418.48Dx = 1.285 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9833 reflections
a = 14.4115 (6) Åθ = 2.4–26.4°
b = 11.4432 (4) ŵ = 0.09 mm1
c = 13.4320 (5) ÅT = 100 K
β = 102.434 (2)°Block-like, colorless
V = 2163.16 (14) Å30.30 × 0.22 × 0.16 mm
Z = 4
Data collection top
Bruker Kappa APEXII CCD area-detector
diffractometer
4460 independent reflections
Radiation source: X-ray tube3365 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.077
φ and ω scansθmax = 26.5°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 1818
Tmin = 0.773, Tmax = 0.986k = 1414
53973 measured reflectionsl = 1616
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-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 reflectionsΔρmax = 0.26 e Å3
283 parametersΔρmin = 0.29 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0027 (6)
Crystal data top
C17H21NO2·C8H5NO2V = 2163.16 (14) Å3
Mr = 418.48Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.4115 (6) ŵ = 0.09 mm1
b = 11.4432 (4) ÅT = 100 K
c = 13.4320 (5) Å0.30 × 0.22 × 0.16 mm
β = 102.434 (2)°
Data collection top
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 = 0.986Rint = 0.077
53973 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.123H-atom parameters constrained
S = 1.08Δρmax = 0.26 e Å3
4460 reflectionsΔρmin = 0.29 e Å3
283 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.78847 (9)0.26899 (10)1.27242 (9)0.0198 (3)
O20.42137 (9)0.55754 (10)0.63528 (9)0.0214 (3)
O30.36128 (9)0.47288 (10)0.45967 (9)0.0231 (3)
H30.38670.48420.52130.035*
O40.41806 (9)0.29167 (10)0.49454 (9)0.0228 (3)
N10.59803 (10)0.44438 (12)0.89741 (10)0.0153 (3)
N20.14883 (12)0.20871 (16)0.04889 (13)0.0330 (4)
C10.47803 (12)0.52251 (14)0.71540 (13)0.0164 (4)
C20.53097 (12)0.41614 (14)0.72134 (13)0.0170 (4)
H20.52590.36930.66200.020*
C30.58791 (12)0.38094 (14)0.80941 (13)0.0166 (4)
H3A0.62210.30980.81040.020*
C40.55015 (12)0.54816 (14)0.89433 (13)0.0171 (4)
H40.55750.59360.95470.021*
C50.49304 (13)0.58744 (14)0.80811 (13)0.0184 (4)
H50.46190.66040.80900.022*
C60.65233 (12)0.40105 (14)0.99267 (13)0.0157 (4)
C70.64668 (12)0.28313 (14)1.01624 (13)0.0167 (4)
H70.60960.23120.96850.020*
C80.69520 (12)0.24247 (15)1.10915 (13)0.0173 (4)
H80.69320.16161.12440.021*
C90.74727 (12)0.31799 (14)1.18134 (13)0.0165 (4)
C100.75397 (12)0.43574 (14)1.15666 (13)0.0186 (4)
H100.79050.48791.20460.022*
C110.70714 (12)0.47612 (14)1.06199 (13)0.0182 (4)
H110.71270.55591.04450.022*
C120.83844 (13)0.34508 (15)1.35125 (13)0.0216 (4)
H12A0.79410.40361.36910.026*
H12B0.88940.38711.32700.026*
C130.88061 (13)0.27279 (15)1.44329 (13)0.0201 (4)
H13A0.92730.21721.42580.024*
H13B0.82980.22711.46440.024*
C140.92947 (13)0.35037 (15)1.53098 (13)0.0212 (4)
H14A0.88220.40531.54820.025*
H14B0.97910.39721.50860.025*
C150.97504 (13)0.28175 (15)1.62619 (13)0.0202 (4)
H15A1.01590.21991.60690.024*
H15B0.92430.24301.65340.024*
C161.03466 (13)0.35659 (16)1.71004 (14)0.0239 (4)
H16A1.06540.30511.76680.029*
H16B1.08560.39511.68290.029*
C170.97755 (14)0.44982 (17)1.75139 (15)0.0281 (5)
H17A0.95490.50821.69830.042*
H17B1.01790.48781.81050.042*
H17C0.92300.41341.77190.042*
C180.37320 (12)0.36264 (14)0.43596 (13)0.0180 (4)
C190.32482 (12)0.33306 (14)0.32950 (13)0.0167 (4)
C200.34235 (12)0.22445 (14)0.29059 (14)0.0186 (4)
H200.38480.17150.33190.022*
C210.29854 (13)0.19297 (15)0.19244 (14)0.0212 (4)
H210.31090.11880.16620.025*
C220.23637 (12)0.27047 (15)0.13243 (13)0.0187 (4)
C230.21814 (13)0.37975 (15)0.17067 (14)0.0213 (4)
H230.17550.43260.12950.026*
C240.26244 (12)0.40992 (15)0.26823 (13)0.0198 (4)
H240.25040.48420.29430.024*
C250.18831 (13)0.23658 (16)0.03127 (15)0.0228 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0267 (7)0.0127 (6)0.0174 (7)0.0011 (5)0.0010 (5)0.0006 (5)
O20.0315 (7)0.0106 (6)0.0192 (7)0.0019 (5)0.0007 (6)0.0009 (5)
O30.0384 (8)0.0089 (6)0.0190 (7)0.0028 (5)0.0008 (6)0.0006 (5)
O40.0311 (7)0.0118 (6)0.0235 (7)0.0027 (5)0.0014 (6)0.0037 (5)
N10.0204 (8)0.0071 (7)0.0180 (8)0.0000 (6)0.0030 (6)0.0000 (6)
N20.0338 (10)0.0377 (10)0.0268 (10)0.0023 (8)0.0050 (8)0.0061 (8)
C10.0222 (9)0.0091 (8)0.0178 (9)0.0030 (7)0.0041 (7)0.0019 (7)
C20.0229 (10)0.0093 (8)0.0186 (9)0.0005 (7)0.0039 (8)0.0028 (7)
C30.0219 (9)0.0080 (8)0.0197 (9)0.0007 (7)0.0044 (8)0.0023 (7)
C40.0242 (10)0.0062 (8)0.0214 (9)0.0001 (7)0.0059 (8)0.0020 (7)
C50.0265 (10)0.0074 (8)0.0214 (9)0.0011 (7)0.0055 (8)0.0002 (7)
C60.0192 (9)0.0118 (8)0.0156 (9)0.0015 (7)0.0028 (7)0.0002 (7)
C70.0207 (9)0.0097 (8)0.0196 (9)0.0009 (7)0.0042 (7)0.0040 (7)
C80.0210 (9)0.0076 (8)0.0235 (10)0.0007 (7)0.0053 (8)0.0001 (7)
C90.0186 (9)0.0133 (8)0.0170 (9)0.0019 (7)0.0027 (7)0.0012 (7)
C100.0233 (10)0.0110 (8)0.0201 (9)0.0028 (7)0.0017 (8)0.0035 (7)
C110.0242 (10)0.0082 (8)0.0217 (10)0.0021 (7)0.0039 (8)0.0002 (7)
C120.0282 (10)0.0139 (9)0.0199 (10)0.0028 (8)0.0008 (8)0.0019 (7)
C130.0241 (10)0.0150 (9)0.0205 (10)0.0005 (7)0.0036 (8)0.0013 (7)
C140.0265 (10)0.0148 (9)0.0203 (10)0.0000 (7)0.0008 (8)0.0018 (7)
C150.0224 (10)0.0162 (9)0.0215 (10)0.0001 (7)0.0038 (8)0.0010 (7)
C160.0265 (10)0.0207 (9)0.0220 (10)0.0001 (8)0.0002 (8)0.0003 (8)
C170.0337 (12)0.0248 (10)0.0251 (10)0.0013 (9)0.0045 (9)0.0032 (8)
C180.0222 (10)0.0102 (8)0.0227 (10)0.0009 (7)0.0073 (8)0.0029 (7)
C190.0208 (9)0.0098 (8)0.0208 (9)0.0016 (7)0.0071 (8)0.0015 (7)
C200.0232 (10)0.0094 (8)0.0239 (10)0.0011 (7)0.0069 (8)0.0030 (7)
C210.0275 (10)0.0117 (8)0.0255 (10)0.0009 (7)0.0085 (8)0.0024 (7)
C220.0214 (9)0.0160 (9)0.0197 (9)0.0028 (7)0.0064 (8)0.0004 (7)
C230.0231 (10)0.0146 (9)0.0254 (10)0.0011 (7)0.0035 (8)0.0026 (7)
C240.0254 (10)0.0089 (8)0.0249 (10)0.0001 (7)0.0049 (8)0.0008 (7)
C250.0245 (10)0.0189 (9)0.0257 (11)0.0017 (8)0.0069 (9)0.0005 (8)
Geometric parameters (Å, º) top
O1—C91.360 (2)C12—H12A0.9900
O1—C121.439 (2)C12—H12B0.9900
O2—C11.268 (2)C13—C141.521 (2)
O3—C181.321 (2)C13—H13A0.9900
O3—H30.8400C13—H13B0.9900
O4—C181.216 (2)C14—C151.524 (2)
N1—C31.368 (2)C14—H14A0.9900
N1—C41.370 (2)C14—H14B0.9900
N1—C61.437 (2)C15—C161.524 (2)
N2—C251.149 (2)C15—H15A0.9900
C1—C51.426 (2)C15—H15B0.9900
C1—C21.430 (2)C16—C171.523 (3)
C2—C31.348 (2)C16—H16A0.9900
C2—H20.9500C16—H16B0.9900
C3—H3A0.9500C17—H17A0.9800
C4—C51.345 (2)C17—H17B0.9800
C4—H40.9500C17—H17C0.9800
C5—H50.9500C18—C191.489 (3)
C6—C111.383 (2)C19—C201.392 (2)
C6—C71.392 (2)C19—C241.393 (2)
C7—C81.374 (2)C20—C211.381 (2)
C7—H70.9500C20—H200.9500
C8—C91.392 (2)C21—C221.388 (2)
C8—H80.9500C21—H210.9500
C9—C101.396 (2)C22—C231.398 (2)
C10—C111.384 (2)C22—C251.439 (3)
C10—H100.9500C23—C241.372 (2)
C11—H110.9500C23—H230.9500
C12—C131.503 (2)C24—H240.9500
C9—O1—C12117.70 (13)C14—C13—H13B109.5
C18—O3—H3109.5H13A—C13—H13B108.1
C3—N1—C4118.34 (14)C13—C14—C15113.15 (14)
C3—N1—C6121.51 (14)C13—C14—H14A108.9
C4—N1—C6120.03 (14)C15—C14—H14A108.9
O2—C1—C5121.70 (15)C13—C14—H14B108.9
O2—C1—C2123.72 (15)C15—C14—H14B108.9
C5—C1—C2114.58 (15)H14A—C14—H14B107.8
C3—C2—C1121.34 (15)C14—C15—C16113.77 (15)
C3—C2—H2119.3C14—C15—H15A108.8
C1—C2—H2119.3C16—C15—H15A108.8
C2—C3—N1122.09 (15)C14—C15—H15B108.8
C2—C3—H3A119.0C16—C15—H15B108.8
N1—C3—H3A119.0H15A—C15—H15B107.7
C5—C4—N1121.77 (15)C17—C16—C15113.57 (15)
C5—C4—H4119.1C17—C16—H16A108.9
N1—C4—H4119.1C15—C16—H16A108.9
C4—C5—C1121.82 (16)C17—C16—H16B108.9
C4—C5—H5119.1C15—C16—H16B108.9
C1—C5—H5119.1H16A—C16—H16B107.7
C11—C6—C7120.13 (16)C16—C17—H17A109.5
C11—C6—N1120.53 (15)C16—C17—H17B109.5
C7—C6—N1119.31 (15)H17A—C17—H17B109.5
C8—C7—C6119.43 (16)C16—C17—H17C109.5
C8—C7—H7120.3H17A—C17—H17C109.5
C6—C7—H7120.3H17B—C17—H17C109.5
C7—C8—C9121.02 (16)O4—C18—O3124.09 (16)
C7—C8—H8119.5O4—C18—C19122.93 (15)
C9—C8—H8119.5O3—C18—C19112.97 (14)
O1—C9—C8115.85 (15)C20—C19—C24119.21 (16)
O1—C9—C10124.91 (15)C20—C19—C18118.57 (15)
C8—C9—C10119.24 (16)C24—C19—C18122.22 (15)
C11—C10—C9119.69 (16)C21—C20—C19120.56 (16)
C11—C10—H10120.2C21—C20—H20119.7
C9—C10—H10120.2C19—C20—H20119.7
C6—C11—C10120.40 (16)C20—C21—C22119.51 (16)
C6—C11—H11119.8C20—C21—H21120.2
C10—C11—H11119.8C22—C21—H21120.2
O1—C12—C13108.79 (14)C21—C22—C23120.46 (16)
O1—C12—H12A109.9C21—C22—C25119.68 (16)
C13—C12—H12A109.9C23—C22—C25119.84 (16)
O1—C12—H12B109.9C24—C23—C22119.35 (17)
C13—C12—H12B109.9C24—C23—H23120.3
H12A—C12—H12B108.3C22—C23—H23120.3
C12—C13—C14110.70 (14)C23—C24—C19120.91 (16)
C12—C13—H13A109.5C23—C24—H24119.5
C14—C13—H13A109.5C19—C24—H24119.5
C12—C13—H13B109.5N2—C25—C22178.9 (2)
O2—C1—C2—C3177.75 (16)C7—C6—C11—C102.4 (3)
C5—C1—C2—C31.7 (2)N1—C6—C11—C10175.36 (15)
C1—C2—C3—N10.1 (3)C9—C10—C11—C61.3 (3)
C4—N1—C3—C21.6 (2)C9—O1—C12—C13178.21 (14)
C6—N1—C3—C2174.49 (16)O1—C12—C13—C14176.75 (14)
C3—N1—C4—C51.0 (2)C12—C13—C14—C15179.12 (15)
C6—N1—C4—C5175.07 (16)C13—C14—C15—C16172.79 (15)
N1—C4—C5—C10.9 (3)C14—C15—C16—C1762.7 (2)
O2—C1—C5—C4177.24 (16)O4—C18—C19—C209.2 (3)
C2—C1—C5—C42.2 (2)O3—C18—C19—C20171.44 (15)
C3—N1—C6—C11142.83 (17)O4—C18—C19—C24170.38 (17)
C4—N1—C6—C1141.2 (2)O3—C18—C19—C249.0 (2)
C3—N1—C6—C739.4 (2)C24—C19—C20—C210.0 (3)
C4—N1—C6—C7136.59 (17)C18—C19—C20—C21179.57 (15)
C11—C6—C7—C80.6 (3)C19—C20—C21—C220.2 (3)
N1—C6—C7—C8177.14 (15)C20—C21—C22—C230.1 (3)
C6—C7—C8—C92.2 (3)C20—C21—C22—C25178.06 (16)
C12—O1—C9—C8176.54 (15)C21—C22—C23—C240.1 (3)
C12—O1—C9—C103.5 (2)C25—C22—C23—C24178.26 (16)
C7—C8—C9—O1176.83 (15)C22—C23—C24—C190.3 (3)
C7—C8—C9—C103.2 (3)C20—C19—C24—C230.2 (3)
O1—C9—C10—C11178.61 (16)C18—C19—C24—C23179.35 (16)
C8—C9—C10—C111.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O20.841.722.5244 (17)159
C2—H2···O40.952.603.438 (2)147
C4—H4···O4i0.952.373.148 (2)139
C7—H7···O2ii0.952.413.303 (2)156
C8—H8···O3ii0.952.483.273 (2)140
C13—H13B···Cg3iii0.992.913.856 (2)161
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2; (iii) x, y1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC17H21NO2·C8H5NO2
Mr418.48
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)14.4115 (6), 11.4432 (4), 13.4320 (5)
β (°) 102.434 (2)
V3)2163.16 (14)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.30 × 0.22 × 0.16
Data collection
DiffractometerBruker Kappa APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.773, 0.986
No. of measured, independent and
observed [I > 2σ(I)] reflections
53973, 4460, 3365
Rint0.077
(sin θ/λ)max1)0.627
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.123, 1.08
No. of reflections4460
No. of parameters283
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O20.841.722.5244 (17)159
C2—H2···O40.952.603.438 (2)147
C4—H4···O4i0.952.373.148 (2)139
C7—H7···O2ii0.952.413.303 (2)156
C8—H8···O3ii0.952.483.273 (2)140
C13—H13B···Cg3iii0.992.913.856 (2)161
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x+1, y1/2, z+3/2; (iii) x, y1/2, z1/2.
 

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