Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017538/sk3500sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017538/sk3500Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017538/sk3500IIsup3.hkl |
CCDC references: 964810; 964811
Neurodegenerative diseases, such as Alzheimer's and Parkinson's, are growing in incidence with the increase in life expectancy of the human population. They remain an unmet clinical need, and the search for new targets and effective treatments with disease-modifying properties is still an incomplete endeavour.
Monoamine oxidase (MAO), a mammalian enzyme present in two isoforms (MAO-A and MAO-B), is an attractive drug target as it plays a central role in neurotransmitter metabolism. In fact, MAO-B inhibitors are relevant drugs in the therapy of Parkinson's disease (Edmondson et al., 2004; Youdim & Buccafusco, 2005; Riederer et al., 2004) as they have the capacity to prolong the action of dopamine in the brain. However, the MAO-B inhibitors that are currently used in therapy have several associated side effects as they are of the irreversible type [The inhibitors or the side effects?] (Gaspar, Reis et al., 2011; Gaspar, Silva et al., 2011; Gaspar, Teixeira et al., 2011; Reis et al., 2012). Therefore, there is still a great need for the discovery of MAO-B inhibitors with an enhanced and a safer pharmacological profile.
The chromone scaffold has emerged as a fruitful approach to the discovery of novel drugs as it allows the attainment of a versatile chemistry platform and putative potent and selective agents for a range of different biological targets. In fact, the chromone scaffold has been the central core in diverse medicinal chemistry programmes (Alcaro et al., 2010; Gaspar, Reis, Kachler et al., 2012), for the development of novel MAO-B inhibitors (Alcaro et al., 2010; Gaspar, Reis et al., 2011; Gaspar, Silva et al., 2011; Gaspar, Teixeira et al., 2011) as well as of adenosine receptor ligands (Gaspar, Reis, Kachler et al., 2012; Gaspar, Reis, Matos et al., 2012). In this context, the structural characterization of the polymorphic forms of the title novel chromone carboxamide derivative, (I), is presented in this work. Unequivocal characterization of chromones is of the utmost importance in medicinal chemistry projects as it allows the speeding up of studies of structure–activity relationships and molecular docking. In fact, polymorphism has a special relevance in pharmaceutical processing and formulation due to its impact on key drug properties, such as dissolution rate and stability.
Crystal data, data collection and structure refinement details are summarized in Table 1.
All chemicals were of analysis grade and were purchased from Sigma–Aldrich Química S.A. (Sintra, Portugal) and used without additional purification.
For the synthesis of (I), POCl3 (2.6 mmol) was added to a solution of chromone-3-carboxylic acid (1.3 mmol) in dimethylformamide (2 ml). The mixture was stirred at room temperature for 30 min, resulting in the formation of the corresponding acyl chloride in situ. 2-Methoxyaniline (1.9 mmol) was then added and the solution stirred for 1 h. The mixture was then diluted with dichloromethane (20 ml) and washed with H2O (3 × 10 ml) and saturated NaHCO3 solution (3 × 10 ml). The organic phase was dried with Na2SO4, filtered and concentrated under reduced pressure. Crystals of (I) suitable for X-ray diffraction were obtained by recrystallization from ethyl acetate (for polymorph A) or CH2Cl2/n-hexane [Solvent ratio?] (for polymorph B).
H atoms were located in difference maps and treated as riding atoms, with aromatic C—H = 0.95 Å and N—H = 0.88 Å, with Uiso(H) = 1.2Ueq(C), and with methyl C—H = 0.98 Å, with Uiso(H) = 1.5Ueq(C). The positions of the N-bound H atom and the methyl groups were checked on a final difference map.
The title compound, (I), crystallizes in two polymorphic forms (Figs. 1 and 2), referred to as polymorphs A and B. In both structures, the compound crystallizes in the space group P21/c with two molecules (1 and 2) in the asymmetric unit. Here, atom labels have the general notation nx, where n = 1 or 2 referring to molecules 1 or 2 and x refers to the numbering of the atom, so that molecules 1 are labelled 1x and molecules 2 as 2x, in both polymorphs.
Molecular conformation may be the most relevant information that solid-state X-ray analysis can give with respect to the prediction of pharmacological activity of chromones and to give an insight concerning their structure–activity profiles, while the supramolecular strucure may condition the bioavailability of the compound. The conformation of these molecules is driven by the carboxamide residue: they exhibit an anti configuration with respect to the C—N rotamer of the amide, which allows for the establishment of three or four intramolecular hydrogen bonds. As can be seen by the information given in Table 1 and Fig. 3, amide atom Nn3 acts as a donor to the O atom of the methoxy group and to the carbonyl O atom of the chromone ring. This donation allows the formation of a six-membered S(5) ring (R3 in Fig. 3) and a five-membered S(6) ring (R1), respectively (Bernstein et al., 1995). Also, the amide O atom acts as an acceptor for a weak hydrogen-bond interaction (Cn36—Hn36···On3; ortho position of the benzyl ring), forming another S(6) ring (Fig. 3). A fourth hydrogen-bond interaction involving the amide O atom may also be considered, viz. Cn2—Hn2(ortho-chromene), giving an S(5) ring (Fig. 3).
There are slight differences in geometry between the molecules, although the hydrogen-bonding network restrains their geometry, particularly the rotation of the aromatic rings around the carboxamide group. The chromone rings are mostly planar, as expected. For polymorph A, the mean planes formed by all the non-H atoms of the chromone ring in molecules 1 and 2 have maximum deviations of -0.020 (1) and -0.017 (1) Å, respectively, for atoms C14 and C24, while for polymorph B the corresponding values are -0.044 (4) and -0.011 (4) Å, respectively, for atoms C12 and C27. Table 3 gives the values calculated for the dihedral angles between the mean planes of the chromone and benzene rings, θ1, between the mean plane of the chromone and the plane defined by atoms On31/Cn37/Nn3, θ2, and between the mean plane of the benzene ring and that defined by atoms On31/Cn37/Nn3 of the amide group, θ3. Molecule 2 of polymorph A is practically planar, whereas the remaining ones present slight torsions between the defined planes. In molecule 2 of polymorph B, the amide group is practically coplanar with the chromone ring, with the overall deviation from planarity being due to the torsion of the benzene substituent in relation to the On31—Cn37—Nn3 residue. In contrast, the deviations from planarity that both molecules 1 exhibit are due to some degree of bending of the Cα and Cα' atoms (Cn31 and Cn3) out of the On31—Cn37—Nn3 plane of the amide. This bending is followed by a lengthening of the internal hydrogen-bond contacts involving carbonyl atom O131, thus making the pseudo-rings R2 and R4 less flat in these molecules.
The differences in conformation between molecules 1 and 2 of the polymorphs can be assessed by the quaternion fit method (Mackay, 1984), which fits molecule 1 onto molecule 2 of polymorph A with a rotation angle of -174° about the (pseudo)axis, giving a weighted fit of 0.131 Å and a unit weight r.m.s. fit of 0.137 Å for 22 fitted atoms. In polymorph B, molecule 1 fits onto molecule 2 with a rotation angle of -31° about the (pseudo)axis, with a weighted fit of 0.187 Å and a unit weight r.m.s. fit of 0.181 Å for the 22 fitted atoms (Figs. 4 and 5). Table 3 gives the quaternion fit parameters for all pairs of molecules. These values indicate that the differences in conformation are slightly greater for the molecules 1 and 2 of polymorph B and these differences can be appreciated graphically in Figs. 4 and 5. However, when the molecules of polymorph A are compared with those of polymorph B (Table 3), it can be seen that molecule 1 of polymorph A is very close in conformation to molecule 2 of polymorph B and, to a lesser extent, the conformation of molecule 2 of polymorph A is close to that of molecule 1 of polymorph B.
It is interesting to compare the internal hydrogen-bond network presented by this compound with the analogous N-(2-methoxyphenyl)-4-oxo-4H-2-chromone carboxamide (Gomes et al., 2013) having the same configuration (see Fig. 6). As can be seen, the amidic substitution at the 3-position of the chromone system `inverts' the relative position of the O-atom pair On1/On4 of the chromone ring with respect to the phenylamide, compared with the structure of the 2-chromone carboxamide. From a structural point of view, this inversion permits the formation of two pseudo-six-membered rings in the chrom-3-one, in contrast with one pseudo-six-membered ring and one pseudo-five-membered ring in the 2-substituted compound. Moreover, in the 3-substituted compound, the acceptor for the N-bound H atom is the oxo O atom of the chromone ring, instead of the heteroatom in the 2-substituted compounds. These differences suggest that 3-substituted chromones may be structurally more stable than their 2-substituted analogues. These particular differences may also determine the availability for docking when their pharmacological activities are kept in mind.
In polymorph A, the molecules of the selected asymmetric unit are linked by weak C12—H12···O231 and C22—H22···O131 hydrogen bonds to form dimers (Fig. 1). In polymorph B, the molecules within the selected asymmetric unit are connected by a weak C25—H25···O11 hydrogen bond.
Details for both compounds are given in Table 2. There are no intermolecular hydrogen bonds in polymorph A other than those which form the dimer described above. The supramolecular structure is determined by π–π stacking interactions as described below. In polymorph B, the supramolecular hydrogen-bond pattern is best described in terms of the individual structures which comprise it. As described above, the molecules within the selected asymmetric unit are connected by a weak C25—H25···O11 hydrogen bond. The molecules in the asymmetric unit are linked to form a centrosymmetric R44(24) quadrimer [tetramer?] across a centre of symmetry at (1/2, 1/2, 1/2) by a C22—H22···O131 hydrogen bond (Fig. 7). In addition, the molecules in the asymmetric unit are linked by a weak C16—H16···O231(x + 1, y, z) hydrogen bond to form C22(13) chains, which run parallel to the a axis (Fig. 8). A weak C133—H133···O132(x, -y + 3/2, z + 1/2) hydrogen bond links molecules 1 into a C(4) chain produced by the action of a c-glide at y = 3/4 which runs along the c axis (Fig. 9).
Table 5 gives details for the π–π stacking parameters between the chromone rings in both compounds. In all cases, packing takes place between centrosymetrically related molecules of the same type. Views of the packing perpendicular to the chromone rings are shown in Fig. 10 for polymorph A and in Fig. 11 for polymorph B. In polymorph A, in the case of molecule 2, there is a possible interaction between the chromone ring and the 2-methoxyphenyl ring at (-x + 1, -y + 1, -z + 1). The pyran ring is inclined to this latter ring at an angle of 2.82 (6)° [centroid separation 3.5263 (10) Å] and to the benzene ring of the chromone system at 2.14 (6)° [centroid separation 3.6509 (11) Å]. In all cases, the perpendicular distances between the centroids and the planes are less than 3.5 Å.
There are similar interactions between the chromone and methoxyphenyl rings in polymorph B, where the centroid-to-centroid distance is less than 4 Å but the angles between the planes lie in the range 5–11°. In all cases, the perpendicular distances between the centroids and the planes are less than 3.5 Å. This overlap of rings for molecule 2 is shown in Fig. 7.
For related literature, see: Alcaro et al. (2010); Bernstein et al. (1995); Edmondson et al. (2004); Gaspar, Reis, Fonseca, Milhazes, Vina, Uriarte & Borges (2011); Gaspar, Reis, Kachler, Paoletta, Uriarte, Klotz, Moro & Borges (2012); Gaspar, Reis, Matos, Uriarte & Borges (2012); Gaspar, Silva, Yanez, Vina, Orallo, Ortuso, Uriarte, Alcaro & Borges (2011); Gaspar, Teixeira, Uriarte, Milhazes, Melo, Cordeiro, Ortuso, Alcaro & Borges (2011); Gomes et al. (2013); Mackay (1984); Reis et al. (2012); Riederer et al. (2004); Youdim & Buccafusco (2005).
For both compounds, data collection: CrystalClear-SM Expert (Rigaku, 2011); cell refinement: CrystalClear-SM Expert (Rigaku, 2011); data reduction: CrystalClear-SM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: OSCAIL (McArdle et al., 2004) and SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OSCAIL (McArdle et al., 2004) and SHELXL97 (Sheldrick, 2008).
C17H13NO4 | F(000) = 1232 |
Mr = 295.28 | Dx = 1.424 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ybc | Cell parameters from 7383 reflections |
a = 8.9867 (18) Å | θ = 2.4–30.1° |
b = 20.669 (4) Å | µ = 0.10 mm−1 |
c = 14.856 (3) Å | T = 100 K |
β = 93.545 (4)° | Block, colourless |
V = 2754.2 (9) Å3 | 0.24 × 0.18 × 0.05 mm |
Z = 8 |
Rigaku Saturn724+ diffractometer | 7417 independent reflections |
Radiation source: rotating anode | 6703 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.028 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 30.1°, θmin = 2.5° |
profile data from ω scans | h = −12→9 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | k = −28→28 |
Tmin = 0.976, Tmax = 0.995 | l = −19→20 |
24297 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0474P)2 + 1.2245P] where P = (Fo2 + 2Fc2)/3 |
7417 reflections | (Δ/σ)max = 0.001 |
399 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C17H13NO4 | V = 2754.2 (9) Å3 |
Mr = 295.28 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.9867 (18) Å | µ = 0.10 mm−1 |
b = 20.669 (4) Å | T = 100 K |
c = 14.856 (3) Å | 0.24 × 0.18 × 0.05 mm |
β = 93.545 (4)° |
Rigaku Saturn724+ diffractometer | 7417 independent reflections |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | 6703 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.995 | Rint = 0.028 |
24297 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.34 e Å−3 |
7417 reflections | Δρmin = −0.26 e Å−3 |
399 parameters |
Experimental. 1H and 13C NMR spectra of samples, in CDCl3, were recorded at room temperature in 5mm outside diameter (o.d.) tubes. Tetramethylsilane (TMS) was used as an internal standard, chemical shifts are expressed in p.p.m. (δ) and J in Hz. One-dimensional 13C NMR was recorded on a Bruker AMX 400 NMR spectrometer operating at 100MHz, typically with a 30° pulse flip angle, a pulse repetition time of 4.8 s, and a spectral width of 31 250 Hz with 32 K data points. For the DEPT sequence, the width of the 90° pulse for 13C was 4 µs, and that of the 90° pulse for 1H was 9.5°; the delay 2J C,H/1 was set to 3.5 µs. Spectra were collected in the t1 domain in 256 experiments with 2 K data points and spectral widths of 5050 and 27 669Hz in the F2(1H) and F2(13C) dimensions, respectively. The relaxation delay D1 was set to 2 s. The data have been processed using sine-bell weighting functions in both dimensions. A mass spectrum was obtained using a Hewlett–Packard 5988A spectrometer. N-(2-methoxyphenyl)-4-oxo-4H-chromene-3-carboxamide: yield: 52%; 1H NMR (CDCl3, δ, p.p.m.): 4.02 (s, 3H), 6.95 (dd, J = 8.1 and 1.4 Hz, 1H), 7.00 (td, J = 7.6 and 1.1 Hz, 1H), 7.13-7.06 (m, 1H), 7.52 (ddd, J = 8.1, 7.2 and 1.1 Hz, 1H), 7.58 (dd, J = 8.5 and 0.6 Hz, 1H), 7.77 (ddd, J = 8.7, 7.1 and 1.7 Hz, 1H), 8.40-8.34 (m, 1H), 8.53 (dd, J = 8.0 and 1.6 Hz, 1H), 9.07 (s, 1H), 11.70 (s, 1H); 13C NMR (CDCl3, δ, p.p.m.): 56.2, 110.4, 116.6, 118.6, 121.0, 121.1, 124.3, 126.45, 126.54, 128.1, 134.8, 142.9, 156.3, 160.7, 162.9, 177.3. MS m/z(%) (ESI): 295(M+, 59), 264 (11), 187 (10), 173 (100), 121 (44). |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O11 | 0.58072 (10) | 0.55610 (5) | 0.16260 (6) | 0.01977 (19) | |
O131 | 0.19155 (11) | 0.62562 (5) | 0.25077 (6) | 0.0238 (2) | |
O14 | 0.27278 (11) | 0.62781 (5) | −0.02677 (6) | 0.0232 (2) | |
O132 | −0.05197 (11) | 0.70644 (5) | −0.01921 (7) | 0.0285 (2) | |
N13 | 0.08753 (12) | 0.64098 (5) | 0.10799 (7) | 0.0193 (2) | |
H13 | 0.1024 | 0.6347 | 0.0506 | 0.023* | |
C14A | 0.51381 (15) | 0.58579 (6) | 0.00828 (9) | 0.0185 (2) | |
C18A | 0.61512 (15) | 0.56094 (6) | 0.07405 (9) | 0.0184 (2) | |
C12 | 0.44833 (14) | 0.57823 (6) | 0.18573 (9) | 0.0190 (2) | |
H12 | 0.4281 | 0.5762 | 0.2477 | 0.023* | |
C13 | 0.34071 (14) | 0.60327 (6) | 0.12775 (9) | 0.0181 (2) | |
C14 | 0.36595 (15) | 0.60760 (6) | 0.03191 (9) | 0.0185 (2) | |
C15 | 0.55592 (15) | 0.58818 (6) | −0.08112 (9) | 0.0217 (3) | |
H15 | 0.4887 | 0.6052 | −0.1270 | 0.026* | |
C16 | 0.69393 (16) | 0.56612 (7) | −0.10289 (9) | 0.0239 (3) | |
H16 | 0.7214 | 0.5675 | −0.1636 | 0.029* | |
C17 | 0.79343 (16) | 0.54160 (7) | −0.03503 (10) | 0.0242 (3) | |
H17 | 0.8888 | 0.5268 | −0.0501 | 0.029* | |
C18 | 0.75513 (15) | 0.53865 (7) | 0.05345 (9) | 0.0217 (3) | |
H18 | 0.8228 | 0.5218 | 0.0992 | 0.026* | |
C131 | −0.05113 (14) | 0.66753 (6) | 0.12815 (9) | 0.0188 (2) | |
C132 | −0.12700 (15) | 0.70253 (7) | 0.05784 (9) | 0.0217 (3) | |
C133 | −0.26539 (15) | 0.72957 (7) | 0.07000 (10) | 0.0254 (3) | |
H133 | −0.3160 | 0.7533 | 0.0226 | 0.030* | |
C134 | −0.32990 (15) | 0.72173 (7) | 0.15240 (10) | 0.0255 (3) | |
H134 | −0.4243 | 0.7405 | 0.1613 | 0.031* | |
C135 | −0.25708 (15) | 0.68674 (7) | 0.22111 (10) | 0.0239 (3) | |
H135 | −0.3026 | 0.6810 | 0.2766 | 0.029* | |
C136 | −0.11717 (15) | 0.65982 (6) | 0.20948 (9) | 0.0206 (3) | |
H136 | −0.0672 | 0.6362 | 0.2572 | 0.025* | |
C138 | −0.12357 (19) | 0.73863 (8) | −0.09510 (11) | 0.0328 (3) | |
H13A | −0.2179 | 0.7168 | −0.1124 | 0.049* | |
H13B | −0.0586 | 0.7374 | −0.1457 | 0.049* | |
H13C | −0.1434 | 0.7837 | −0.0793 | 0.049* | |
C137 | 0.20050 (14) | 0.62411 (6) | 0.16870 (9) | 0.0186 (2) | |
O21 | 0.09282 (10) | 0.59246 (4) | 0.47465 (6) | 0.01993 (19) | |
O231 | 0.36612 (11) | 0.48270 (5) | 0.33124 (6) | 0.0247 (2) | |
O24 | 0.29544 (12) | 0.43766 (5) | 0.60396 (7) | 0.0275 (2) | |
O232 | 0.55100 (11) | 0.32563 (5) | 0.55228 (6) | 0.0227 (2) | |
N23 | 0.43100 (12) | 0.41546 (5) | 0.44957 (7) | 0.0184 (2) | |
H23 | 0.4136 | 0.4076 | 0.5062 | 0.022* | |
C22 | 0.18795 (14) | 0.55393 (6) | 0.43330 (9) | 0.0184 (2) | |
H22 | 0.2064 | 0.5638 | 0.3725 | 0.022* | |
C28A | 0.06638 (14) | 0.57942 (6) | 0.56290 (9) | 0.0183 (2) | |
C23 | 0.25952 (14) | 0.50227 (6) | 0.47128 (8) | 0.0176 (2) | |
C24A | 0.13439 (14) | 0.52780 (6) | 0.60930 (9) | 0.0194 (3) | |
C24 | 0.23671 (14) | 0.48460 (6) | 0.56433 (9) | 0.0193 (3) | |
C25 | 0.10273 (16) | 0.51836 (7) | 0.69948 (10) | 0.0255 (3) | |
H25 | 0.1484 | 0.4837 | 0.7328 | 0.031* | |
C26 | 0.00585 (17) | 0.55905 (8) | 0.73998 (10) | 0.0297 (3) | |
H26 | −0.0147 | 0.5524 | 0.8013 | 0.036* | |
C27 | −0.06260 (16) | 0.61012 (7) | 0.69144 (10) | 0.0268 (3) | |
H27 | −0.1301 | 0.6377 | 0.7198 | 0.032* | |
C28 | −0.03276 (15) | 0.62065 (6) | 0.60302 (10) | 0.0220 (3) | |
H28 | −0.0788 | 0.6554 | 0.5699 | 0.026* | |
C231 | 0.53231 (14) | 0.37398 (6) | 0.40980 (9) | 0.0179 (2) | |
C232 | 0.59772 (14) | 0.32550 (6) | 0.46620 (9) | 0.0184 (2) | |
C233 | 0.70050 (14) | 0.28289 (6) | 0.43362 (9) | 0.0209 (3) | |
H233 | 0.7449 | 0.2505 | 0.4719 | 0.025* | |
C234 | 0.73838 (15) | 0.28778 (6) | 0.34444 (10) | 0.0220 (3) | |
H234 | 0.8085 | 0.2585 | 0.3219 | 0.026* | |
C235 | 0.67471 (15) | 0.33496 (7) | 0.28847 (9) | 0.0216 (3) | |
H235 | 0.7012 | 0.3379 | 0.2277 | 0.026* | |
C236 | 0.57197 (15) | 0.37824 (6) | 0.32078 (9) | 0.0205 (3) | |
H236 | 0.5289 | 0.4107 | 0.2821 | 0.025* | |
C238 | 0.61362 (17) | 0.27814 (7) | 0.61341 (10) | 0.0271 (3) | |
H23A | 0.5901 | 0.2348 | 0.5899 | 0.041* | |
H23B | 0.5716 | 0.2834 | 0.6723 | 0.041* | |
H23C | 0.7221 | 0.2837 | 0.6200 | 0.041* | |
C237 | 0.35733 (14) | 0.46628 (6) | 0.41011 (9) | 0.0182 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0206 (4) | 0.0231 (4) | 0.0156 (4) | 0.0013 (4) | 0.0013 (3) | 0.0019 (3) |
O131 | 0.0256 (5) | 0.0301 (5) | 0.0158 (5) | 0.0054 (4) | 0.0021 (4) | 0.0038 (4) |
O14 | 0.0262 (5) | 0.0260 (5) | 0.0171 (5) | 0.0049 (4) | −0.0008 (4) | 0.0025 (4) |
O132 | 0.0257 (5) | 0.0373 (6) | 0.0221 (5) | 0.0013 (4) | −0.0007 (4) | 0.0114 (4) |
N13 | 0.0207 (5) | 0.0220 (5) | 0.0151 (5) | 0.0003 (4) | 0.0006 (4) | 0.0000 (4) |
C14A | 0.0225 (6) | 0.0158 (6) | 0.0173 (6) | −0.0018 (5) | 0.0012 (5) | 0.0001 (4) |
C18A | 0.0230 (6) | 0.0170 (5) | 0.0154 (6) | −0.0029 (5) | 0.0014 (5) | −0.0004 (4) |
C12 | 0.0205 (6) | 0.0187 (6) | 0.0180 (6) | −0.0011 (5) | 0.0030 (5) | 0.0010 (5) |
C13 | 0.0213 (6) | 0.0160 (5) | 0.0169 (6) | −0.0006 (5) | 0.0011 (5) | 0.0004 (4) |
C14 | 0.0238 (6) | 0.0153 (5) | 0.0164 (6) | −0.0001 (5) | 0.0005 (5) | 0.0008 (4) |
C15 | 0.0265 (7) | 0.0215 (6) | 0.0172 (6) | 0.0006 (5) | 0.0016 (5) | 0.0012 (5) |
C16 | 0.0280 (7) | 0.0263 (7) | 0.0179 (6) | −0.0012 (5) | 0.0041 (5) | −0.0011 (5) |
C17 | 0.0223 (6) | 0.0268 (7) | 0.0240 (7) | −0.0002 (5) | 0.0042 (5) | −0.0024 (5) |
C18 | 0.0211 (6) | 0.0235 (6) | 0.0204 (6) | −0.0001 (5) | −0.0003 (5) | −0.0007 (5) |
C131 | 0.0185 (6) | 0.0164 (5) | 0.0211 (6) | −0.0018 (5) | −0.0013 (5) | −0.0008 (5) |
C132 | 0.0226 (6) | 0.0205 (6) | 0.0217 (7) | −0.0042 (5) | −0.0008 (5) | 0.0024 (5) |
C133 | 0.0230 (6) | 0.0207 (6) | 0.0315 (8) | −0.0006 (5) | −0.0061 (5) | 0.0027 (5) |
C134 | 0.0197 (6) | 0.0234 (6) | 0.0329 (8) | 0.0004 (5) | −0.0020 (5) | −0.0050 (6) |
C135 | 0.0216 (6) | 0.0258 (7) | 0.0243 (7) | −0.0019 (5) | 0.0011 (5) | −0.0059 (5) |
C136 | 0.0212 (6) | 0.0207 (6) | 0.0195 (6) | −0.0017 (5) | −0.0020 (5) | −0.0017 (5) |
C138 | 0.0379 (8) | 0.0360 (8) | 0.0235 (7) | −0.0007 (7) | −0.0066 (6) | 0.0097 (6) |
C137 | 0.0221 (6) | 0.0154 (5) | 0.0182 (6) | −0.0004 (5) | 0.0011 (5) | 0.0028 (4) |
O21 | 0.0228 (4) | 0.0188 (4) | 0.0182 (5) | 0.0031 (4) | 0.0015 (3) | 0.0008 (3) |
O231 | 0.0322 (5) | 0.0245 (5) | 0.0182 (5) | 0.0064 (4) | 0.0072 (4) | 0.0049 (4) |
O24 | 0.0323 (5) | 0.0307 (5) | 0.0201 (5) | 0.0122 (4) | 0.0057 (4) | 0.0081 (4) |
O232 | 0.0270 (5) | 0.0232 (5) | 0.0179 (5) | 0.0053 (4) | 0.0018 (4) | 0.0036 (4) |
N23 | 0.0195 (5) | 0.0209 (5) | 0.0150 (5) | 0.0025 (4) | 0.0021 (4) | 0.0012 (4) |
C22 | 0.0199 (6) | 0.0186 (6) | 0.0169 (6) | −0.0004 (5) | 0.0022 (5) | −0.0007 (5) |
C28A | 0.0170 (6) | 0.0192 (6) | 0.0189 (6) | −0.0037 (5) | 0.0018 (4) | −0.0008 (5) |
C23 | 0.0173 (6) | 0.0191 (6) | 0.0164 (6) | −0.0007 (5) | 0.0011 (4) | 0.0004 (5) |
C24A | 0.0172 (6) | 0.0215 (6) | 0.0196 (6) | −0.0010 (5) | 0.0023 (5) | 0.0002 (5) |
C24 | 0.0179 (6) | 0.0220 (6) | 0.0181 (6) | −0.0002 (5) | 0.0007 (5) | 0.0017 (5) |
C25 | 0.0255 (7) | 0.0297 (7) | 0.0218 (7) | 0.0030 (6) | 0.0059 (5) | 0.0043 (5) |
C26 | 0.0307 (7) | 0.0364 (8) | 0.0230 (7) | 0.0031 (6) | 0.0108 (6) | 0.0023 (6) |
C27 | 0.0231 (6) | 0.0284 (7) | 0.0299 (8) | 0.0015 (6) | 0.0082 (6) | −0.0038 (6) |
C28 | 0.0194 (6) | 0.0199 (6) | 0.0266 (7) | 0.0001 (5) | 0.0017 (5) | −0.0013 (5) |
C231 | 0.0168 (5) | 0.0181 (6) | 0.0186 (6) | −0.0004 (5) | −0.0002 (4) | −0.0019 (5) |
C232 | 0.0184 (6) | 0.0189 (6) | 0.0179 (6) | −0.0022 (5) | −0.0005 (5) | −0.0007 (5) |
C233 | 0.0202 (6) | 0.0174 (6) | 0.0248 (7) | 0.0010 (5) | −0.0014 (5) | −0.0006 (5) |
C234 | 0.0196 (6) | 0.0199 (6) | 0.0267 (7) | 0.0000 (5) | 0.0021 (5) | −0.0049 (5) |
C235 | 0.0218 (6) | 0.0241 (6) | 0.0192 (6) | −0.0004 (5) | 0.0027 (5) | −0.0035 (5) |
C236 | 0.0223 (6) | 0.0209 (6) | 0.0182 (6) | −0.0002 (5) | 0.0001 (5) | −0.0007 (5) |
C238 | 0.0353 (8) | 0.0253 (7) | 0.0202 (7) | 0.0067 (6) | −0.0016 (6) | 0.0038 (5) |
C237 | 0.0185 (6) | 0.0191 (6) | 0.0172 (6) | −0.0011 (5) | 0.0014 (4) | 0.0003 (5) |
O11—C12 | 1.3392 (16) | O21—C22 | 1.3443 (15) |
O11—C18A | 1.3734 (15) | O21—C28A | 1.3735 (15) |
O131—C137 | 1.2271 (16) | O231—C237 | 1.2270 (16) |
O14—C14 | 1.2431 (16) | O24—C24 | 1.2361 (16) |
O132—C132 | 1.3663 (17) | O232—C232 | 1.3704 (16) |
O132—C138 | 1.4276 (17) | O232—C238 | 1.4288 (16) |
N13—C137 | 1.3611 (16) | N23—C237 | 1.3555 (16) |
N13—C131 | 1.4106 (17) | N23—C231 | 1.4070 (16) |
N13—H13 | 0.88 | N23—H23 | 0.88 |
C14A—C18A | 1.3919 (18) | C22—C23 | 1.3518 (18) |
C14A—C15 | 1.4041 (18) | C22—H22 | 0.9500 |
C14A—C14 | 1.4662 (18) | C28A—C24A | 1.3909 (18) |
C18A—C18 | 1.3917 (19) | C28A—C28 | 1.3933 (18) |
C12—C13 | 1.3573 (18) | C23—C24 | 1.4565 (18) |
C12—H12 | 0.9500 | C23—C237 | 1.5001 (18) |
C13—C14 | 1.4583 (18) | C24A—C25 | 1.4002 (18) |
C13—C137 | 1.4960 (18) | C24A—C24 | 1.4715 (18) |
C15—C16 | 1.3785 (19) | C25—C26 | 1.376 (2) |
C15—H15 | 0.9500 | C25—H25 | 0.9500 |
C16—C17 | 1.400 (2) | C26—C27 | 1.399 (2) |
C16—H16 | 0.9500 | C26—H26 | 0.9500 |
C17—C18 | 1.3805 (19) | C27—C28 | 1.374 (2) |
C17—H17 | 0.9500 | C27—H27 | 0.9500 |
C18—H18 | 0.9500 | C28—H28 | 0.9500 |
C131—C136 | 1.3878 (18) | C231—C236 | 1.3936 (18) |
C131—C132 | 1.4112 (18) | C231—C232 | 1.4109 (18) |
C132—C133 | 1.385 (2) | C232—C233 | 1.3850 (18) |
C133—C134 | 1.396 (2) | C233—C234 | 1.3919 (19) |
C133—H133 | 0.9500 | C233—H233 | 0.9500 |
C134—C135 | 1.382 (2) | C234—C235 | 1.3823 (19) |
C134—H134 | 0.9500 | C234—H234 | 0.9500 |
C135—C136 | 1.3955 (19) | C235—C236 | 1.3920 (18) |
C135—H135 | 0.9500 | C235—H235 | 0.9500 |
C136—H136 | 0.9500 | C236—H236 | 0.9500 |
C138—H13A | 0.9800 | C238—H23A | 0.9800 |
C138—H13B | 0.9800 | C238—H23B | 0.9800 |
C138—H13C | 0.9800 | C238—H23C | 0.9800 |
C12—O11—C18A | 118.50 (10) | C22—O21—C28A | 118.19 (10) |
C132—O132—C138 | 117.87 (12) | C232—O232—C238 | 117.41 (11) |
C137—N13—C131 | 126.25 (11) | C237—N23—C231 | 127.02 (11) |
C137—N13—H13 | 116.9 | C237—N23—H23 | 116.5 |
C131—N13—H13 | 116.9 | C231—N23—H23 | 116.5 |
C18A—C14A—C15 | 118.30 (12) | O21—C22—C23 | 125.23 (12) |
C18A—C14A—C14 | 120.56 (12) | O21—C22—H22 | 117.4 |
C15—C14A—C14 | 121.13 (12) | C23—C22—H22 | 117.4 |
O11—C18A—C18 | 116.53 (11) | O21—C28A—C24A | 121.80 (11) |
O11—C18A—C14A | 121.54 (12) | O21—C28A—C28 | 116.18 (12) |
C18—C18A—C14A | 121.92 (12) | C24A—C28A—C28 | 122.02 (12) |
O11—C12—C13 | 125.23 (12) | C22—C23—C24 | 120.19 (12) |
O11—C12—H12 | 117.4 | C22—C23—C237 | 114.85 (11) |
C13—C12—H12 | 117.4 | C24—C23—C237 | 124.94 (11) |
C12—C13—C14 | 119.69 (12) | C28A—C24A—C25 | 118.16 (12) |
C12—C13—C137 | 115.89 (12) | C28A—C24A—C24 | 120.54 (12) |
C14—C13—C137 | 124.42 (11) | C25—C24A—C24 | 121.29 (12) |
O14—C14—C13 | 124.51 (12) | O24—C24—C23 | 124.59 (12) |
O14—C14—C14A | 121.10 (12) | O24—C24—C24A | 121.36 (12) |
C13—C14—C14A | 114.39 (11) | C23—C24—C24A | 114.04 (11) |
C16—C15—C14A | 120.62 (12) | C26—C25—C24A | 120.32 (13) |
C16—C15—H15 | 119.7 | C26—C25—H25 | 119.8 |
C14A—C15—H15 | 119.7 | C24A—C25—H25 | 119.8 |
C15—C16—C17 | 119.64 (13) | C25—C26—C27 | 120.38 (14) |
C15—C16—H16 | 120.2 | C25—C26—H26 | 119.8 |
C17—C16—H16 | 120.2 | C27—C26—H26 | 119.8 |
C18—C17—C16 | 121.04 (13) | C28—C27—C26 | 120.44 (13) |
C18—C17—H17 | 119.5 | C28—C27—H27 | 119.8 |
C16—C17—H17 | 119.5 | C26—C27—H27 | 119.8 |
C17—C18—C18A | 118.48 (13) | C27—C28—C28A | 118.67 (13) |
C17—C18—H18 | 120.8 | C27—C28—H28 | 120.7 |
C18A—C18—H18 | 120.8 | C28A—C28—H28 | 120.7 |
C136—C131—N13 | 124.83 (12) | C236—C231—N23 | 124.76 (12) |
C136—C131—C132 | 119.36 (12) | C236—C231—C232 | 119.13 (12) |
N13—C131—C132 | 115.78 (12) | N23—C231—C232 | 116.11 (11) |
O132—C132—C133 | 125.38 (12) | O232—C232—C233 | 125.22 (12) |
O132—C132—C131 | 114.18 (12) | O232—C232—C231 | 114.35 (11) |
C133—C132—C131 | 120.45 (13) | C233—C232—C231 | 120.43 (12) |
C132—C133—C134 | 119.50 (13) | C232—C233—C234 | 119.61 (12) |
C132—C133—H133 | 120.3 | C232—C233—H233 | 120.2 |
C134—C133—H133 | 120.3 | C234—C233—H233 | 120.2 |
C135—C134—C133 | 120.33 (13) | C235—C234—C233 | 120.48 (12) |
C135—C134—H134 | 119.8 | C235—C234—H234 | 119.8 |
C133—C134—H134 | 119.8 | C233—C234—H234 | 119.8 |
C134—C135—C136 | 120.42 (13) | C234—C235—C236 | 120.30 (13) |
C134—C135—H135 | 119.8 | C234—C235—H235 | 119.8 |
C136—C135—H135 | 119.8 | C236—C235—H235 | 119.8 |
C131—C136—C135 | 119.94 (13) | C235—C236—C231 | 120.05 (12) |
C131—C136—H136 | 120.0 | C235—C236—H236 | 120.0 |
C135—C136—H136 | 120.0 | C231—C236—H236 | 120.0 |
O132—C138—H13A | 109.5 | O232—C238—H23A | 109.5 |
O132—C138—H13B | 109.5 | O232—C238—H23B | 109.5 |
H13A—C138—H13B | 109.5 | H23A—C238—H23B | 109.5 |
O132—C138—H13C | 109.5 | O232—C238—H23C | 109.5 |
H13A—C138—H13C | 109.5 | H23A—C238—H23C | 109.5 |
H13B—C138—H13C | 109.5 | H23B—C238—H23C | 109.5 |
O131—C137—N13 | 124.05 (12) | O231—C237—N23 | 124.66 (12) |
O131—C137—C13 | 121.33 (12) | O231—C237—C23 | 121.07 (12) |
N13—C137—C13 | 114.63 (11) | N23—C237—C23 | 114.27 (11) |
C12—O11—C18A—C18 | 178.63 (11) | C28A—O21—C22—C23 | 0.84 (18) |
C12—O11—C18A—C14A | −2.52 (17) | C22—O21—C28A—C24A | −0.34 (17) |
C15—C14A—C18A—O11 | −178.89 (11) | C22—O21—C28A—C28 | 179.90 (11) |
C14—C14A—C18A—O11 | −0.11 (18) | O21—C22—C23—C24 | −0.2 (2) |
C15—C14A—C18A—C18 | −0.09 (19) | O21—C22—C23—C237 | 178.72 (11) |
C14—C14A—C18A—C18 | 178.68 (12) | O21—C28A—C24A—C25 | 179.23 (12) |
C18A—O11—C12—C13 | 2.69 (19) | C28—C28A—C24A—C25 | −1.03 (19) |
O11—C12—C13—C14 | −0.1 (2) | O21—C28A—C24A—C24 | −0.73 (19) |
O11—C12—C13—C137 | 179.13 (11) | C28—C28A—C24A—C24 | 179.02 (12) |
C12—C13—C14—O14 | 177.60 (13) | C22—C23—C24—O24 | 178.77 (13) |
C137—C13—C14—O14 | −1.6 (2) | C237—C23—C24—O24 | 0.0 (2) |
C12—C13—C14—C14A | −2.41 (17) | C22—C23—C24—C24A | −0.81 (17) |
C137—C13—C14—C14A | 178.41 (11) | C237—C23—C24—C24A | −179.63 (12) |
C18A—C14A—C14—O14 | −177.52 (12) | C28A—C24A—C24—O24 | −178.34 (13) |
C15—C14A—C14—O14 | 1.22 (19) | C25—C24A—C24—O24 | 1.7 (2) |
C18A—C14A—C14—C13 | 2.49 (17) | C28A—C24A—C24—C23 | 1.25 (18) |
C15—C14A—C14—C13 | −178.76 (12) | C25—C24A—C24—C23 | −178.70 (12) |
C18A—C14A—C15—C16 | 0.32 (19) | C28A—C24A—C25—C26 | 0.5 (2) |
C14—C14A—C15—C16 | −178.45 (12) | C24—C24A—C25—C26 | −179.50 (14) |
C14A—C15—C16—C17 | −0.5 (2) | C24A—C25—C26—C27 | 0.3 (2) |
C15—C16—C17—C18 | 0.5 (2) | C25—C26—C27—C28 | −0.7 (2) |
C16—C17—C18—C18A | −0.3 (2) | C26—C27—C28—C28A | 0.2 (2) |
O11—C18A—C18—C17 | 178.94 (12) | O21—C28A—C28—C27 | −179.57 (12) |
C14A—C18A—C18—C17 | 0.1 (2) | C24A—C28A—C28—C27 | 0.7 (2) |
C137—N13—C131—C136 | −24.5 (2) | C237—N23—C231—C236 | −1.1 (2) |
C137—N13—C131—C132 | 157.55 (12) | C237—N23—C231—C232 | 178.25 (12) |
C138—O132—C132—C133 | −2.7 (2) | C238—O232—C232—C233 | 0.19 (19) |
C138—O132—C132—C131 | 177.35 (12) | C238—O232—C232—C231 | −179.49 (11) |
C136—C131—C132—O132 | −179.41 (12) | C236—C231—C232—O232 | 179.99 (11) |
N13—C131—C132—O132 | −1.30 (17) | N23—C231—C232—O232 | 0.64 (16) |
C136—C131—C132—C133 | 0.67 (19) | C236—C231—C232—C233 | 0.29 (19) |
N13—C131—C132—C133 | 178.78 (12) | N23—C231—C232—C233 | −179.06 (11) |
O132—C132—C133—C134 | 179.82 (13) | O232—C232—C233—C234 | 179.85 (12) |
C131—C132—C133—C134 | −0.3 (2) | C231—C232—C233—C234 | −0.48 (19) |
C132—C133—C134—C135 | −0.6 (2) | C232—C233—C234—C235 | 0.3 (2) |
C133—C134—C135—C136 | 1.1 (2) | C233—C234—C235—C236 | 0.1 (2) |
N13—C131—C136—C135 | −178.11 (12) | C234—C235—C236—C231 | −0.3 (2) |
C132—C131—C136—C135 | −0.18 (19) | N23—C231—C236—C235 | 179.38 (12) |
C134—C135—C136—C131 | −0.7 (2) | C232—C231—C236—C235 | 0.09 (19) |
C131—N13—C137—O131 | 5.6 (2) | C231—N23—C237—O231 | 2.0 (2) |
C131—N13—C137—C13 | −174.15 (11) | C231—N23—C237—C23 | −178.52 (11) |
C12—C13—C137—O131 | 8.53 (18) | C22—C23—C237—O231 | −1.85 (18) |
C14—C13—C137—O131 | −172.26 (12) | C24—C23—C237—O231 | 177.02 (12) |
C12—C13—C137—N13 | −171.73 (11) | C22—C23—C237—N23 | 178.61 (11) |
C14—C13—C137—N13 | 7.48 (18) | C24—C23—C237—N23 | −2.52 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13···O14 | 0.88 | 1.98 | 2.6954 (15) | 138 |
N13—H13···O132 | 0.88 | 2.24 | 2.5845 (15) | 103 |
N23—H23···O24 | 0.88 | 1.95 | 2.7020 (15) | 142 |
N23—H23···O232 | 0.88 | 2.18 | 2.5952 (15) | 108 |
C12—H12···O131 | 0.95 | 2.36 | 2.7374 (17) | 103 |
C12—H12···O231 | 0.95 | 2.38 | 3.0519 (16) | 127 |
C22—H22···O131 | 0.95 | 2.21 | 3.0921 (17) | 154 |
C22—H22···O231 | 0.95 | 2.31 | 2.7074 (16) | 104 |
C136—H136···O131 | 0.95 | 2.34 | 2.8918 (17) | 116 |
C236—H236···O231 | 0.95 | 2.24 | 2.8538 (17) | 122 |
C17H13NO4 | F(000) = 1232 |
Mr = 295.28 | Dx = 1.411 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ybc | Cell parameters from 5164 reflections |
a = 14.614 (13) Å | θ = 2.2–31.2° |
b = 23.95 (2) Å | µ = 0.10 mm−1 |
c = 8.125 (7) Å | T = 100 K |
β = 102.069 (17)° | Lath, colourless |
V = 2781 (4) Å3 | 0.42 × 0.07 × 0.02 mm |
Z = 8 |
Rigaku Saturn724+ diffractometer | 4410 independent reflections |
Radiation source: rotating anode | 3407 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.066 |
Detector resolution: 28.5714 pixels mm-1 | θmax = 25.0°, θmin = 2.9° |
profile data from ω scans | h = −17→8 |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | k = −28→28 |
Tmin = 0.959, Tmax = 0.998 | l = −7→9 |
9112 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.089 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.19 | w = 1/[σ2(Fo2) + (0.0313P)2 + 3.3953P] where P = (Fo2 + 2Fc2)/3 |
4410 reflections | (Δ/σ)max < 0.001 |
399 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C17H13NO4 | V = 2781 (4) Å3 |
Mr = 295.28 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.614 (13) Å | µ = 0.10 mm−1 |
b = 23.95 (2) Å | T = 100 K |
c = 8.125 (7) Å | 0.42 × 0.07 × 0.02 mm |
β = 102.069 (17)° |
Rigaku Saturn724+ diffractometer | 4410 independent reflections |
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | 3407 reflections with I > 2σ(I) |
Tmin = 0.959, Tmax = 0.998 | Rint = 0.066 |
9112 measured reflections |
R[F2 > 2σ(F2)] = 0.089 | 0 restraints |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.21 e Å−3 |
4410 reflections | Δρmin = −0.26 e Å−3 |
399 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O11 | 0.85050 (19) | 0.54340 (11) | 0.4167 (3) | 0.0261 (7) | |
O14 | 1.0374 (2) | 0.63055 (12) | 0.7691 (3) | 0.0335 (7) | |
O131 | 0.7779 (2) | 0.57666 (14) | 0.8624 (4) | 0.0432 (9) | |
O132 | 1.02878 (19) | 0.69568 (11) | 1.1360 (3) | 0.0278 (7) | |
N13 | 0.8992 (2) | 0.63738 (13) | 0.9462 (4) | 0.0238 (8) | |
H13 | 0.9504 | 0.6503 | 0.9188 | 0.029* | |
C12 | 0.8303 (3) | 0.55851 (16) | 0.5639 (5) | 0.0274 (10) | |
H12 | 0.7708 | 0.5480 | 0.5837 | 0.033* | |
C13 | 0.8875 (3) | 0.58737 (15) | 0.6858 (5) | 0.0215 (9) | |
C14 | 0.9808 (3) | 0.60293 (16) | 0.6646 (5) | 0.0248 (9) | |
C14A | 1.0047 (3) | 0.58316 (15) | 0.5082 (5) | 0.0217 (9) | |
C15 | 1.0943 (3) | 0.59176 (17) | 0.4729 (6) | 0.0305 (10) | |
H15 | 1.1416 | 0.6097 | 0.5534 | 0.037* | |
C16 | 1.1130 (3) | 0.57425 (17) | 0.3221 (5) | 0.0313 (10) | |
H16 | 1.1732 | 0.5803 | 0.2986 | 0.038* | |
C17 | 1.0440 (3) | 0.54759 (17) | 0.2035 (5) | 0.0291 (10) | |
H17 | 1.0575 | 0.5360 | 0.0993 | 0.035* | |
C18 | 0.9566 (3) | 0.53783 (15) | 0.2357 (5) | 0.0256 (9) | |
H18 | 0.9096 | 0.5195 | 0.1554 | 0.031* | |
C18A | 0.9390 (3) | 0.55547 (16) | 0.3889 (5) | 0.0223 (9) | |
C131 | 0.8781 (3) | 0.65819 (15) | 1.0960 (5) | 0.0235 (9) | |
C132 | 0.9477 (3) | 0.69070 (16) | 1.1968 (5) | 0.0244 (9) | |
C133 | 0.9331 (3) | 0.71472 (16) | 1.3441 (5) | 0.0279 (10) | |
H133 | 0.9799 | 0.7377 | 1.4097 | 0.033* | |
C134 | 0.8494 (3) | 0.70496 (16) | 1.3953 (5) | 0.0298 (10) | |
H134 | 0.8393 | 0.7210 | 1.4970 | 0.036* | |
C135 | 0.7808 (3) | 0.67205 (16) | 1.2993 (5) | 0.0276 (10) | |
H135 | 0.7241 | 0.6653 | 1.3359 | 0.033* | |
C136 | 0.7943 (3) | 0.64870 (15) | 1.1489 (5) | 0.0241 (9) | |
H136 | 0.7467 | 0.6264 | 1.0826 | 0.029* | |
C137 | 0.8496 (3) | 0.59976 (16) | 0.8401 (5) | 0.0257 (10) | |
C138 | 1.1057 (3) | 0.72489 (18) | 1.2394 (5) | 0.0385 (12) | |
H13A | 1.0897 | 0.7645 | 1.2451 | 0.058* | |
H13B | 1.1614 | 0.7212 | 1.1907 | 0.058* | |
H13C | 1.1186 | 0.7089 | 1.3530 | 0.058* | |
O21 | 0.45233 (19) | 0.42667 (10) | 0.1389 (3) | 0.0243 (6) | |
O24 | 0.61752 (19) | 0.56118 (11) | 0.3188 (3) | 0.0280 (7) | |
O231 | 0.33787 (19) | 0.54582 (11) | 0.3871 (3) | 0.0282 (7) | |
O232 | 0.59615 (19) | 0.67071 (11) | 0.5794 (4) | 0.0303 (7) | |
N23 | 0.4678 (2) | 0.60146 (12) | 0.4318 (4) | 0.0207 (7) | |
H23 | 0.5245 | 0.6041 | 0.4116 | 0.025* | |
C22 | 0.4206 (3) | 0.46871 (15) | 0.2216 (5) | 0.0231 (9) | |
H22 | 0.3580 | 0.4662 | 0.2366 | 0.028* | |
C23 | 0.4703 (3) | 0.51407 (15) | 0.2852 (5) | 0.0197 (9) | |
C24 | 0.5668 (3) | 0.52078 (15) | 0.2658 (5) | 0.0229 (9) | |
C24A | 0.6003 (3) | 0.47434 (15) | 0.1739 (5) | 0.0212 (9) | |
C25 | 0.6920 (3) | 0.47412 (18) | 0.1443 (5) | 0.0284 (10) | |
H25 | 0.7329 | 0.5045 | 0.1819 | 0.034* | |
C26 | 0.7228 (3) | 0.42988 (19) | 0.0610 (5) | 0.0350 (11) | |
H26 | 0.7849 | 0.4298 | 0.0426 | 0.042* | |
C27 | 0.6634 (3) | 0.38579 (18) | 0.0041 (5) | 0.0325 (11) | |
H27 | 0.6854 | 0.3555 | −0.0527 | 0.039* | |
C28 | 0.5727 (3) | 0.38505 (16) | 0.0287 (5) | 0.0262 (10) | |
H28 | 0.5315 | 0.3551 | −0.0118 | 0.031* | |
C28A | 0.5436 (3) | 0.42991 (16) | 0.1150 (5) | 0.0219 (9) | |
C231 | 0.4380 (3) | 0.64603 (15) | 0.5221 (5) | 0.0214 (9) | |
C232 | 0.5074 (3) | 0.68349 (16) | 0.6012 (5) | 0.0243 (9) | |
C233 | 0.4851 (3) | 0.72817 (16) | 0.6914 (5) | 0.0316 (11) | |
H233 | 0.5328 | 0.7531 | 0.7441 | 0.038* | |
C234 | 0.3926 (3) | 0.73714 (17) | 0.7061 (5) | 0.0345 (11) | |
H234 | 0.3770 | 0.7680 | 0.7683 | 0.041* | |
C235 | 0.3241 (3) | 0.70023 (17) | 0.6286 (5) | 0.0325 (10) | |
H235 | 0.2611 | 0.7060 | 0.6381 | 0.039* | |
C236 | 0.3461 (3) | 0.65470 (16) | 0.5368 (5) | 0.0264 (10) | |
H236 | 0.2983 | 0.6297 | 0.4845 | 0.032* | |
C237 | 0.4186 (3) | 0.55521 (16) | 0.3733 (5) | 0.0204 (9) | |
C238 | 0.6719 (3) | 0.70235 (18) | 0.6756 (6) | 0.0364 (11) | |
H23A | 0.6661 | 0.7414 | 0.6392 | 0.055* | |
H23B | 0.7314 | 0.6872 | 0.6581 | 0.055* | |
H23C | 0.6699 | 0.7001 | 0.7952 | 0.055* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O11 | 0.0274 (17) | 0.0299 (15) | 0.0225 (16) | −0.0042 (13) | 0.0086 (13) | −0.0034 (13) |
O14 | 0.0274 (18) | 0.0423 (18) | 0.0301 (18) | −0.0127 (14) | 0.0043 (13) | −0.0066 (15) |
O131 | 0.037 (2) | 0.060 (2) | 0.0363 (19) | −0.0301 (17) | 0.0176 (15) | −0.0187 (16) |
O132 | 0.0257 (17) | 0.0311 (15) | 0.0245 (16) | −0.0117 (13) | 0.0004 (12) | 0.0009 (13) |
N13 | 0.029 (2) | 0.0211 (16) | 0.0224 (19) | −0.0069 (15) | 0.0067 (15) | −0.0016 (15) |
C12 | 0.035 (3) | 0.026 (2) | 0.024 (2) | −0.0045 (19) | 0.010 (2) | 0.0023 (19) |
C13 | 0.025 (2) | 0.0201 (19) | 0.018 (2) | −0.0024 (17) | 0.0022 (17) | 0.0018 (17) |
C14 | 0.027 (2) | 0.022 (2) | 0.025 (2) | 0.0010 (18) | 0.0039 (19) | 0.0065 (18) |
C14A | 0.019 (2) | 0.0207 (19) | 0.024 (2) | 0.0027 (17) | 0.0017 (17) | 0.0043 (18) |
C15 | 0.026 (3) | 0.031 (2) | 0.034 (3) | 0.0002 (19) | 0.006 (2) | 0.001 (2) |
C16 | 0.025 (3) | 0.033 (2) | 0.039 (3) | 0.001 (2) | 0.013 (2) | 0.004 (2) |
C17 | 0.025 (3) | 0.028 (2) | 0.035 (3) | 0.0039 (19) | 0.008 (2) | 0.001 (2) |
C18 | 0.033 (3) | 0.0184 (19) | 0.025 (2) | 0.0010 (18) | 0.0035 (19) | 0.0006 (18) |
C18A | 0.022 (2) | 0.0207 (19) | 0.026 (2) | 0.0041 (17) | 0.0092 (18) | 0.0038 (17) |
C131 | 0.031 (3) | 0.0178 (19) | 0.021 (2) | −0.0006 (18) | 0.0036 (18) | 0.0058 (17) |
C132 | 0.027 (2) | 0.020 (2) | 0.026 (2) | −0.0032 (18) | 0.0048 (19) | 0.0075 (18) |
C133 | 0.038 (3) | 0.0186 (19) | 0.025 (2) | −0.0041 (19) | 0.0003 (19) | 0.0020 (18) |
C134 | 0.040 (3) | 0.023 (2) | 0.026 (2) | 0.001 (2) | 0.006 (2) | 0.0007 (19) |
C135 | 0.029 (3) | 0.023 (2) | 0.030 (2) | 0.0057 (19) | 0.0059 (19) | −0.0008 (19) |
C136 | 0.028 (2) | 0.019 (2) | 0.023 (2) | 0.0004 (17) | −0.0002 (18) | 0.0009 (17) |
C137 | 0.027 (3) | 0.028 (2) | 0.022 (2) | −0.0057 (19) | 0.0046 (19) | 0.0024 (19) |
C138 | 0.039 (3) | 0.042 (3) | 0.030 (3) | −0.017 (2) | −0.003 (2) | 0.005 (2) |
O21 | 0.0287 (16) | 0.0191 (14) | 0.0269 (16) | −0.0049 (12) | 0.0098 (13) | −0.0057 (12) |
O24 | 0.0229 (16) | 0.0295 (15) | 0.0323 (17) | −0.0052 (13) | 0.0073 (13) | −0.0106 (13) |
O231 | 0.0199 (16) | 0.0358 (16) | 0.0310 (17) | −0.0058 (13) | 0.0103 (13) | −0.0080 (14) |
O232 | 0.0265 (17) | 0.0284 (15) | 0.0366 (18) | −0.0093 (13) | 0.0079 (14) | −0.0123 (14) |
N23 | 0.0217 (19) | 0.0208 (16) | 0.0205 (18) | −0.0033 (14) | 0.0064 (14) | −0.0022 (14) |
C22 | 0.030 (2) | 0.021 (2) | 0.020 (2) | 0.0004 (18) | 0.0100 (18) | −0.0013 (18) |
C23 | 0.022 (2) | 0.0196 (19) | 0.017 (2) | −0.0014 (16) | 0.0026 (16) | −0.0025 (17) |
C24 | 0.026 (2) | 0.022 (2) | 0.019 (2) | −0.0040 (18) | 0.0000 (17) | −0.0023 (18) |
C24A | 0.024 (2) | 0.023 (2) | 0.017 (2) | 0.0010 (17) | 0.0057 (17) | −0.0022 (17) |
C25 | 0.021 (2) | 0.037 (2) | 0.027 (2) | −0.0015 (19) | 0.0032 (18) | −0.010 (2) |
C26 | 0.029 (3) | 0.047 (3) | 0.030 (3) | −0.001 (2) | 0.009 (2) | −0.010 (2) |
C27 | 0.040 (3) | 0.030 (2) | 0.027 (2) | 0.012 (2) | 0.007 (2) | −0.007 (2) |
C28 | 0.033 (3) | 0.020 (2) | 0.025 (2) | −0.0013 (19) | 0.0044 (19) | −0.0003 (18) |
C28A | 0.019 (2) | 0.024 (2) | 0.023 (2) | 0.0011 (17) | 0.0065 (17) | 0.0045 (18) |
C231 | 0.030 (2) | 0.0169 (19) | 0.019 (2) | 0.0043 (17) | 0.0074 (17) | 0.0009 (17) |
C232 | 0.026 (2) | 0.023 (2) | 0.022 (2) | 0.0001 (18) | 0.0032 (18) | −0.0012 (18) |
C233 | 0.044 (3) | 0.020 (2) | 0.031 (3) | 0.001 (2) | 0.008 (2) | −0.0028 (19) |
C234 | 0.049 (3) | 0.026 (2) | 0.030 (3) | 0.012 (2) | 0.011 (2) | −0.004 (2) |
C235 | 0.035 (3) | 0.033 (2) | 0.030 (3) | 0.009 (2) | 0.009 (2) | −0.003 (2) |
C236 | 0.031 (3) | 0.026 (2) | 0.023 (2) | 0.0009 (19) | 0.0079 (19) | −0.0053 (18) |
C237 | 0.027 (2) | 0.021 (2) | 0.011 (2) | 0.0003 (17) | 0.0004 (17) | −0.0002 (16) |
C238 | 0.029 (3) | 0.037 (2) | 0.042 (3) | −0.013 (2) | 0.004 (2) | −0.012 (2) |
O11—C12 | 1.340 (4) | O21—C22 | 1.345 (4) |
O11—C18A | 1.388 (5) | O21—C28A | 1.390 (5) |
O14—C14 | 1.245 (5) | O24—C24 | 1.240 (4) |
O131—C137 | 1.231 (5) | O231—C237 | 1.230 (5) |
O132—C132 | 1.381 (5) | O232—C232 | 1.380 (5) |
O132—C138 | 1.437 (5) | O232—C238 | 1.431 (5) |
N13—C137 | 1.349 (5) | N23—C237 | 1.352 (5) |
N13—C131 | 1.408 (5) | N23—C231 | 1.415 (5) |
N13—H13 | 0.8800 | N23—H23 | 0.8800 |
C12—C13 | 1.346 (5) | C22—C23 | 1.348 (5) |
C12—H12 | 0.9500 | C22—H22 | 0.9500 |
C13—C14 | 1.458 (5) | C23—C24 | 1.460 (5) |
C13—C137 | 1.502 (5) | C23—C237 | 1.510 (5) |
C14—C14A | 1.465 (5) | C24—C24A | 1.478 (5) |
C14A—C18A | 1.383 (5) | C24A—C28A | 1.371 (5) |
C14A—C15 | 1.412 (5) | C24A—C25 | 1.411 (5) |
C15—C16 | 1.375 (6) | C25—C26 | 1.383 (6) |
C15—H15 | 0.9500 | C25—H25 | 0.9500 |
C16—C17 | 1.395 (6) | C26—C27 | 1.384 (6) |
C16—H16 | 0.9500 | C26—H26 | 0.9500 |
C17—C18 | 1.377 (6) | C27—C28 | 1.382 (6) |
C17—H17 | 0.9500 | C27—H27 | 0.9500 |
C18—C18A | 1.388 (5) | C28—C28A | 1.397 (5) |
C18—H18 | 0.9500 | C28—H28 | 0.9500 |
C131—C136 | 1.399 (6) | C231—C236 | 1.389 (5) |
C131—C132 | 1.401 (6) | C231—C232 | 1.405 (5) |
C132—C133 | 1.384 (5) | C232—C233 | 1.374 (5) |
C133—C134 | 1.392 (6) | C233—C234 | 1.398 (6) |
C133—H133 | 0.9500 | C233—H233 | 0.9500 |
C134—C135 | 1.381 (6) | C234—C235 | 1.384 (6) |
C134—H134 | 0.9500 | C234—H234 | 0.9500 |
C135—C136 | 1.395 (5) | C235—C236 | 1.396 (5) |
C135—H135 | 0.9500 | C235—H235 | 0.9500 |
C136—H136 | 0.9500 | C236—H236 | 0.9500 |
C138—H13A | 0.9800 | C238—H23A | 0.9800 |
C138—H13B | 0.9800 | C238—H23B | 0.9800 |
C138—H13C | 0.9800 | C238—H23C | 0.9800 |
C12—O11—C18A | 118.4 (3) | C22—O21—C28A | 117.9 (3) |
C132—O132—C138 | 117.3 (3) | C232—O232—C238 | 116.9 (3) |
C137—N13—C131 | 127.1 (3) | C237—N23—C231 | 127.0 (3) |
C137—N13—H13 | 116.4 | C237—N23—H23 | 116.5 |
C131—N13—H13 | 116.4 | C231—N23—H23 | 116.5 |
O11—C12—C13 | 125.2 (4) | O21—C22—C23 | 125.5 (4) |
O11—C12—H12 | 117.4 | O21—C22—H22 | 117.3 |
C13—C12—H12 | 117.4 | C23—C22—H22 | 117.3 |
C12—C13—C14 | 119.8 (4) | C22—C23—C24 | 120.2 (4) |
C12—C13—C137 | 115.8 (4) | C22—C23—C237 | 115.1 (3) |
C14—C13—C137 | 124.4 (3) | C24—C23—C237 | 124.7 (3) |
O14—C14—C13 | 124.0 (4) | O24—C24—C23 | 124.7 (4) |
O14—C14—C14A | 121.2 (4) | O24—C24—C24A | 121.7 (4) |
C13—C14—C14A | 114.8 (3) | C23—C24—C24A | 113.6 (3) |
C18A—C14A—C15 | 117.7 (4) | C28A—C24A—C25 | 117.6 (4) |
C18A—C14A—C14 | 120.4 (4) | C28A—C24A—C24 | 121.4 (4) |
C15—C14A—C14 | 121.9 (4) | C25—C24A—C24 | 121.0 (4) |
C16—C15—C14A | 120.1 (4) | C26—C25—C24A | 120.3 (4) |
C16—C15—H15 | 119.9 | C26—C25—H25 | 119.8 |
C14A—C15—H15 | 119.9 | C24A—C25—H25 | 119.8 |
C15—C16—C17 | 120.3 (4) | C25—C26—C27 | 120.2 (4) |
C15—C16—H16 | 119.8 | C25—C26—H26 | 119.9 |
C17—C16—H16 | 119.8 | C27—C26—H26 | 119.9 |
C18—C17—C16 | 120.8 (4) | C28—C27—C26 | 121.0 (4) |
C18—C17—H17 | 119.6 | C28—C27—H27 | 119.5 |
C16—C17—H17 | 119.6 | C26—C27—H27 | 119.5 |
C17—C18—C18A | 118.2 (4) | C27—C28—C28A | 117.7 (4) |
C17—C18—H18 | 120.9 | C27—C28—H28 | 121.2 |
C18A—C18—H18 | 120.9 | C28A—C28—H28 | 121.2 |
C14A—C18A—C18 | 122.8 (4) | C24A—C28A—O21 | 121.4 (3) |
C14A—C18A—O11 | 121.3 (3) | C24A—C28A—C28 | 123.2 (4) |
C18—C18A—O11 | 115.8 (3) | O21—C28A—C28 | 115.4 (3) |
C136—C131—C132 | 119.1 (4) | C236—C231—C232 | 118.9 (4) |
C136—C131—N13 | 124.9 (4) | C236—C231—N23 | 124.5 (4) |
C132—C131—N13 | 116.0 (4) | C232—C231—N23 | 116.6 (3) |
O132—C132—C133 | 124.9 (4) | C233—C232—O232 | 125.1 (4) |
O132—C132—C131 | 114.3 (4) | C233—C232—C231 | 120.8 (4) |
C133—C132—C131 | 120.8 (4) | O232—C232—C231 | 114.0 (3) |
C132—C133—C134 | 119.5 (4) | C232—C233—C234 | 120.4 (4) |
C132—C133—H133 | 120.2 | C232—C233—H233 | 119.8 |
C134—C133—H133 | 120.2 | C234—C233—H233 | 119.8 |
C135—C134—C133 | 120.4 (4) | C235—C234—C233 | 118.9 (4) |
C135—C134—H134 | 119.8 | C235—C234—H234 | 120.6 |
C133—C134—H134 | 119.8 | C233—C234—H234 | 120.6 |
C134—C135—C136 | 120.3 (4) | C234—C235—C236 | 121.1 (4) |
C134—C135—H135 | 119.9 | C234—C235—H235 | 119.5 |
C136—C135—H135 | 119.9 | C236—C235—H235 | 119.5 |
C135—C136—C131 | 119.8 (4) | C231—C236—C235 | 119.9 (4) |
C135—C136—H136 | 120.1 | C231—C236—H236 | 120.1 |
C131—C136—H136 | 120.1 | C235—C236—H236 | 120.1 |
O131—C137—N13 | 124.5 (4) | O231—C237—N23 | 124.6 (4) |
O131—C137—C13 | 120.5 (3) | O231—C237—C23 | 120.6 (3) |
N13—C137—C13 | 115.0 (3) | N23—C237—C23 | 114.8 (3) |
O132—C138—H13A | 109.5 | O232—C238—H23A | 109.5 |
O132—C138—H13B | 109.5 | O232—C238—H23B | 109.5 |
H13A—C138—H13B | 109.5 | H23A—C238—H23B | 109.5 |
O132—C138—H13C | 109.5 | O232—C238—H23C | 109.5 |
H13A—C138—H13C | 109.5 | H23A—C238—H23C | 109.5 |
H13B—C138—H13C | 109.5 | H23B—C238—H23C | 109.5 |
C18A—O11—C12—C13 | 3.6 (6) | C28A—O21—C22—C23 | −0.4 (5) |
O11—C12—C13—C14 | −2.1 (6) | O21—C22—C23—C24 | 0.4 (6) |
O11—C12—C13—C137 | 179.8 (3) | O21—C22—C23—C237 | −179.8 (3) |
C12—C13—C14—O14 | 178.4 (4) | C22—C23—C24—O24 | 179.5 (4) |
C137—C13—C14—O14 | −3.6 (6) | C237—C23—C24—O24 | −0.3 (6) |
C12—C13—C14—C14A | −1.9 (5) | C22—C23—C24—C24A | −0.1 (5) |
C137—C13—C14—C14A | 176.1 (3) | C237—C23—C24—C24A | −179.9 (3) |
O14—C14—C14A—C18A | −176.1 (4) | O24—C24—C24A—C28A | −179.7 (4) |
C13—C14—C14A—C18A | 4.3 (5) | C23—C24—C24A—C28A | −0.1 (5) |
O14—C14—C14A—C15 | 3.5 (6) | O24—C24—C24A—C25 | 0.5 (6) |
C13—C14—C14A—C15 | −176.1 (4) | C23—C24—C24A—C25 | −179.9 (4) |
C18A—C14A—C15—C16 | 1.8 (6) | C28A—C24A—C25—C26 | −1.0 (6) |
C14—C14A—C15—C16 | −177.8 (4) | C24—C24A—C25—C26 | 178.8 (4) |
C14A—C15—C16—C17 | −0.4 (6) | C24A—C25—C26—C27 | 0.8 (6) |
C15—C16—C17—C18 | −0.7 (6) | C25—C26—C27—C28 | 0.2 (7) |
C16—C17—C18—C18A | 0.3 (6) | C26—C27—C28—C28A | −1.0 (6) |
C15—C14A—C18A—C18 | −2.3 (6) | C25—C24A—C28A—O21 | 179.9 (3) |
C14—C14A—C18A—C18 | 177.3 (3) | C24—C24A—C28A—O21 | 0.1 (6) |
C15—C14A—C18A—O11 | 177.4 (3) | C25—C24A—C28A—C28 | 0.2 (6) |
C14—C14A—C18A—O11 | −3.0 (5) | C24—C24A—C28A—C28 | −179.6 (4) |
C17—C18—C18A—C14A | 1.2 (6) | C22—O21—C28A—C24A | 0.2 (5) |
C17—C18—C18A—O11 | −178.5 (3) | C22—O21—C28A—C28 | 179.9 (3) |
C12—O11—C18A—C14A | −1.0 (5) | C27—C28—C28A—C24A | 0.8 (6) |
C12—O11—C18A—C18 | 178.7 (3) | C27—C28—C28A—O21 | −178.9 (3) |
C137—N13—C131—C136 | −9.1 (6) | C237—N23—C231—C236 | −13.3 (6) |
C137—N13—C131—C132 | 170.9 (4) | C237—N23—C231—C232 | 166.6 (4) |
C138—O132—C132—C133 | 4.4 (6) | C238—O232—C232—C233 | 8.3 (6) |
C138—O132—C132—C131 | −175.4 (3) | C238—O232—C232—C231 | −171.5 (3) |
C136—C131—C132—O132 | 177.7 (3) | C236—C231—C232—C233 | −0.2 (6) |
N13—C131—C132—O132 | −2.3 (5) | N23—C231—C232—C233 | 179.8 (4) |
C136—C131—C132—C133 | −2.0 (6) | C236—C231—C232—O232 | 179.6 (3) |
N13—C131—C132—C133 | 177.9 (3) | N23—C231—C232—O232 | −0.4 (5) |
O132—C132—C133—C134 | −177.7 (4) | O232—C232—C233—C234 | −179.7 (4) |
C131—C132—C133—C134 | 2.1 (6) | C231—C232—C233—C234 | 0.0 (6) |
C132—C133—C134—C135 | −0.7 (6) | C232—C233—C234—C235 | 0.1 (6) |
C133—C134—C135—C136 | −0.7 (6) | C233—C234—C235—C236 | −0.1 (6) |
C134—C135—C136—C131 | 0.7 (6) | C232—C231—C236—C235 | 0.3 (6) |
C132—C131—C136—C135 | 0.7 (6) | N23—C231—C236—C235 | −179.8 (4) |
N13—C131—C136—C135 | −179.3 (3) | C234—C235—C236—C231 | −0.1 (6) |
C131—N13—C137—O131 | −1.9 (7) | C231—N23—C237—O231 | 2.0 (6) |
C131—N13—C137—C13 | 177.5 (3) | C231—N23—C237—C23 | −178.4 (3) |
C12—C13—C137—O131 | 11.6 (6) | C22—C23—C237—O231 | 1.7 (5) |
C14—C13—C137—O131 | −166.4 (4) | C24—C23—C237—O231 | −178.5 (4) |
C12—C13—C137—N13 | −167.8 (4) | C22—C23—C237—N23 | −177.9 (3) |
C14—C13—C137—N13 | 14.1 (5) | C24—C23—C237—N23 | 1.8 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13···O14 | 0.88 | 1.99 | 2.718 (5) | 139 |
N13—H13···O132 | 0.88 | 2.18 | 2.587 (4) | 108 |
N23—H23···O24 | 0.88 | 1.98 | 2.720 (4) | 142 |
N23—H23···O232 | 0.88 | 2.21 | 2.601 (4) | 106 |
C25—H25···O11 | 0.95 | 2.47 | 3.297 (5) | 146 |
C12—H12···O131 | 0.95 | 2.35 | 2.726 (5) | 103 |
C22—H22···O231 | 0.95 | 2.32 | 2.713 (5) | 104 |
C136—H136···O131 | 0.95 | 2.27 | 2.868 (5) | 120 |
C236—H236···O231 | 0.95 | 2.28 | 2.869 (5) | 120 |
C16—H16···O231i | 0.95 | 2.50 | 3.289 (6) | 140 |
C22—H22···O131ii | 0.95 | 2.23 | 3.040 (5) | 142 |
C133—H133···O132iii | 0.95 | 2.43 | 3.286 (5) | 151 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1; (iii) x, −y+3/2, z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C17H13NO4 | C17H13NO4 |
Mr | 295.28 | 295.28 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 8.9867 (18), 20.669 (4), 14.856 (3) | 14.614 (13), 23.95 (2), 8.125 (7) |
β (°) | 93.545 (4) | 102.069 (17) |
V (Å3) | 2754.2 (9) | 2781 (4) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 |
Crystal size (mm) | 0.24 × 0.18 × 0.05 | 0.42 × 0.07 × 0.02 |
Data collection | ||
Diffractometer | Rigaku Saturn724+ diffractometer | Rigaku Saturn724+ diffractometer |
Absorption correction | Multi-scan (CrystalClear-SM Expert; Rigaku, 2011) | Multi-scan (CrystalClear-SM Expert; Rigaku, 2011) |
Tmin, Tmax | 0.976, 0.995 | 0.959, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24297, 7417, 6703 | 9112, 4410, 3407 |
Rint | 0.028 | 0.066 |
(sin θ/λ)max (Å−1) | 0.706 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.119, 1.09 | 0.089, 0.161, 1.19 |
No. of reflections | 7417 | 4410 |
No. of parameters | 399 | 399 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.26 | 0.21, −0.26 |
Computer programs: CrystalClear-SM Expert (Rigaku, 2011), SHELXS97 (Sheldrick, 2008), OSCAIL (McArdle et al., 2004) and SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13···O14 | 0.88 | 1.98 | 2.6954 (15) | 138 |
N13—H13···O132 | 0.88 | 2.24 | 2.5845 (15) | 103 |
N23—H23···O24 | 0.88 | 1.95 | 2.7020 (15) | 142 |
N23—H23···O232 | 0.88 | 2.18 | 2.5952 (15) | 108 |
C12—H12···O131 | 0.95 | 2.36 | 2.7374 (17) | 103 |
C12—H12···O231 | 0.95 | 2.38 | 3.0519 (16) | 127 |
C22—H22···O131 | 0.95 | 2.21 | 3.0921 (17) | 154 |
C22—H22···O231 | 0.95 | 2.31 | 2.7074 (16) | 104 |
C136—H136···O131 | 0.95 | 2.34 | 2.8918 (17) | 116 |
C236—H236···O231 | 0.95 | 2.24 | 2.8538 (17) | 122 |
D—H···A | D—H | H···A | D···A | D—H···A |
N13—H13···O14 | 0.88 | 1.99 | 2.718 (5) | 139 |
N13—H13···O132 | 0.88 | 2.18 | 2.587 (4) | 108 |
N23—H23···O24 | 0.88 | 1.98 | 2.720 (4) | 142 |
N23—H23···O232 | 0.88 | 2.21 | 2.601 (4) | 106 |
C25—H25···O11 | 0.95 | 2.47 | 3.297 (5) | 146 |
C12—H12···O131 | 0.95 | 2.35 | 2.726 (5) | 103 |
C22—H22···O231 | 0.95 | 2.32 | 2.713 (5) | 104 |
C136—H136···O131 | 0.95 | 2.27 | 2.868 (5) | 120 |
C236—H236···O231 | 0.95 | 2.28 | 2.869 (5) | 120 |
C16—H16···O231i | 0.95 | 2.50 | 3.289 (6) | 140 |
C22—H22···O131ii | 0.95 | 2.23 | 3.040 (5) | 142 |
C133—H133···O132iii | 0.95 | 2.43 | 3.286 (5) | 151 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1; (iii) x, −y+3/2, z+1/2. |
θ1 is the dihedral angle between the mean planes of the chromene system and the benzene ring. θ2 is the dihedral angle between the mean plane of the chromone ring and the plane defined by atoms O3/C41/N3. θ3 is the dihedral angle between the mean plane of the phenyl ring and the plane defined by atoms O3/C41/N3. |
Compound | θ1 | θ2 | θ3 |
Polymorph A | |||
Molecule 1 | 11.64 (5) | 8.72 (14) | 20.35 (13) |
Molecule 2 | 2.47 (5) | 1.75 (2) | 2.2 (2) |
Polymorph B | |||
Molecule 1 | 6.50 (18) | 15.0 (5) | 10.1 (6) |
Molecule 2 | 10.52 (17) | 1.8 (6) | 12.27 (6) |
Column A is the fit rotation angle about the (pseudo)axis [l,m,n]. Columns B and C are, respectively, the weighted and unit weight r.m.s. fits. The asterisk (*) denotes an inverted molecule. |
Molecules | A | B | C |
A1—A2 | 174 | 0.131 | 0.137 |
B1—B2 | 31 | 0.187 | 0.181 |
A1—B1 | -121 | 0.173 | 0.171 |
A1—B2 | -109 | 0.046 | 0.071 |
A2*—B1 | 31 | 0.097 | 0.105 |
A2—B2 | -168 | 0.147 | 0.135 |
Cg1, Cg2, Cg5 and Cg6 are the centroids of the rings containing atoms O11, C15, O21 and C25, respectively. In (A), the planes in molecule 1* are inclined at an angle of 0.09 (6)° and those in molecule 2** at 0.79 (6)°. In (B), the planes in molecule 2** are inclined at 0.66 (18)°. The perpendicular distances marked with an asterisk (* or **) are average values. |
π–π | Centroid-to-centroid ditsance (Å) | Perpendicular distance between rings (Å) | Slippage (Å) |
Polymorph A | |||
Cg1···Cg2(-x+1, -y+1, -z) | 3.4421 (10) | 3.3636* | 0.731* |
Cg2···Cg2(-x+1, -y+1, -z) | 3.8640 (11) | 3.3729 (6) | 1.885 |
Cg5···Cg5(-x, -y+1, -z+1) | 3.3830(10 | 3.143 (5) | 0.679 |
Cg5···Cg6(-x, -y+1, -z+1) | 3.7596 (11) | 3.327** | 1.942** |
Polymorph B | |||
Cg1···Cg1(-x+2, -y+1, -z+1) | 4.354 (4) | 3.4119 (15) | 2.705 |
Cg2···Cg2(-x+2, -y+1, -z+1) | 4.063 (4) | 3.4114 (16) | 2.206 |
Cg5···Cg5(-x+1, -y+1, -z) | 3.468 (4) | 3.3235 (15) | 0.991 |
Cg5···Cg6(-x+1, -y+1, -z) | 3.663 (4) | 3.245** | 1.635** |
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