Concomitant polymorphism and a temperature-dependent phase change in (E)-[1-(4-methoxyphenyl)-3-phenyl-2-propenyl­idene­amino]oxyacetic acid

The title compound, C₁₈H₁₇NO₄, crystallizes from ethanol at ambient temperature as two concomitant polymorphs (I) and (II), both monoclinic P2₁/c with Z′ = 1. The less abundant form (I) undergoes a reversible phase-transition at ca 173 K to a third monoclinic polymorph (III), P2₁/n, with Z′ = 2, while the more abundant polymorph (II) is unchanged down to 120 K. In each polymorph of (I)–(III) the molecules are linked by pairs of O—H⋯O hydrogen bonds into cyclic dimers which are crystallographically centrosymmetric in (I) and (II), and approximately, but not crystallographically, centrosymmetric in (III). There are no direction-specific interactions between the hydrogen-bonded dimers in polymorph (I); in polymorph (II) the dimers are linked into sheets by C—H⋯N and C—H⋯π(arene) hydrogen bonds; in polymorph (III) the dimers are linked into chains by a C—H⋯π(arene) hydrogen bond. The interconversion of polymorphs (I) and (III) is a simple displacive phase transition.

1. Introduction

Persulfate oxidation of imino-oxyacetic acids, R¹R²C=NOCH₂COOH, provides a useful route to iminyl radicals (Forrester et al., 1979). The subsequent reactions of the iminyl radicals thus generated depend greatly on the substituents and important species including nitrogen-containing heterocycles can result. We have recently reported the molecular and supramolecular structures of several substituted imino-oxyacetic acids, where the principal mode of supramolecular aggregation is the formation of the cyclic hydrogen-bonded dimers characteristic of simple carboxylic acids (Glidewell et al., 2004a,b). Continuing this study, we have now investigated the title compound which proves to occur in several polymorphic forms. When the title compound was crystallized from ethanol, a mixture of two crystalline forms, concomitant polymorphs (Bernstein et al., 1999), was obtained. These two forms, denoted (I) and (II), are both monoclinic at ambient temperature, with Z′ = 1 in space group P2₁/c; while they have similar unit-cell volumes, their cell dimensions differ markedly and the polymorph with the longer a dimension we denote as polymorph (I). The structure of polymorph (II) has been determined both at 120 (2) and 291 (2) K, and these structure determinations, denoted (IIa) and (IIb), respectively, are essentially identical; hence, for this polymorph we only discuss the results of refinement (IIa). However, when polymorph (I) is cooled to 120 (2) K, it forms a third monoclinic polymorph in P2₁/n with Z′ = 2, denoted (III). The numbering of polymorphs (I)–(III) follows the order in which they were characterized. The supramolecular structures of polymorphs (I)–(III) are briefly compared with those of the analogous compounds (IV)–(VI).

2. Experimental

2.1. Synthesis

The title compound was prepared by the reaction of chloroacetic acid with the oxime derived from (E)-4-MeOC₆H₄Ch=CHCOPh (Atmaram et al., 1982); crystallization from ethanol at ambient temperature gave a mixture of polymorphs (I) and (II). Detailed X-ray examination of a representative sample of the crystals from this mixture indicated that the abundance ratio of (I):(II) was approximately 1:4.

2.2. Data collection, structure solution and refinement

Diffraction data for polymorph (I) and the data set for (II) denoted (IIb) were collected on a Bruker SMART diffractometer at 291 (2) K; diffraction data for (III) and the dataset for (II) denoted (IIa) were collected at 120 (2) K using a Nonius Kappa-CCD diffractometer: in all cases graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) was employed. Other details of cell data, data collection and refinement are summarized in Table 1, together with details of the software employed (Blessing, 1995, 1997; Bruker, 1998, 2000; Ferguson, 1999; McArdle, 2003; Nonius, 1997; Otwinowski & Minor, 1997; Sheldrick, 1997).

Table 1
Experimental details

	(I)	(IIa)	(IIb)	(III)
Crystal data
Chemical formula	C18H17NO4	C18H17NO4	C18H17NO4	C18H17NO4
Mr	311.33	311.33	311.33	311.33
Cell setting, space group	Monoclinic, P21/c	Monoclinic, P21/c	Monoclinic, P21/c	Monoclinic, P21/n
a, b, c (Å)	8.5153 (7), 16.0591 (13), 12.1476 (10)	6.4499 (2), 14.9693 (5), 16.6559 (6)	6.4238 (3), 15.1513 (9), 17.0552 (9)	12.1552 (4), 15.8657 (4), 16.6708 (5)
β (°)	96.801 (2)	92.947 (2)	93.167 (2)	97.4250 (15)
V (Å^3)	1649.5 (2)	1606.01 (9)	1657.43 (15)	3188.02 (16)
Z, Z′	4, 1	4, 1	4, 1	8, 2
Dx (Mg m^−3)	1.254	1.288	1.248	1.297
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
No. of reflections for cell parameters	5963	3690	3837	7291
θ range (°)	2.1–32.6	3.0–27.5	1.8–27.6	3.1–27.5
μ (mm^−1)	0.09	0.09	0.09	0.09
Temperature (K)	291 (2)	120 (2)	291 (2)	120 (2)
Crystal form, colour	Plate, colourless	Plate, yellow	Plate, colourless	Lath, colourless
Crystal size (mm)	0.45 × 0.40 × 0.04	0.25 × 0.20 × 0.05	0.25 × 0.20 × 0.05	0.50 × 0.40 × 0.10
Data collection
Diffractometer	Bruker SMART 1000 CCD area detector	Kappa-CCD	Bruker SMART 1000 CCD area detector	Bruker–Nonius 95 mm CCD camera on κ-goniostat
Data collection method	φ–ω	φ scans, and ω scans with κ offsets	φ–ω	φ and ω scans
Absorption correction	Multi-scan	Multi-scan	Multi-scan	Multi-scan
Tmin	0.952	0.967	0.982	0.950
Tmax	0.996	0.995	0.996	0.991
No. of measured, independent and observed reflections	16 995, 5963, 1586	17 758, 3690, 2647	13 953, 3837, 2171	37 246, 7291, 4714
Criterion for observed reflections	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)	I > 2σ(I)
Rint	0.058	0.062	0.038	0.060
θmax (°)	32.6	27.5	27.6	27.5
Range of h, k, l	−12 → h → 12	−8 → h → 8	−7 → h → 8	−15 → h → 15
	−16 → k → 24	−19 → k → 19	−19 → k → 19	−20 → k → 20
	−17 → l → 18	−21 → l → 16	−22 → l → 21	−21 → l → 21
Refinement
Refinement on	F^2	F^2	F^2	F^2
R[F^2 > 2σ(F^2)], wR(F^2), S	0.056, 0.172, 0.86	0.058, 0.232, 1.14	0.049, 0.151, 0.98	0.048, 0.133, 1.03
No. of reflections	5963	3690	3837	7291
No. of parameters	210	210	210	419
H-atom treatment	Constrained to parent site	Constrained to parent site	Constrained to parent site	Constrained to parent site
Weighting scheme	w = 1/[σ^2(Fo^2) + (0.0654P)^2], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.1318P)^2 + 0.4171P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0795P)^2 + 0.0527P], where P = (Fo^2 + 2Fc^2)/3	w = 1/[σ^2(Fo^2) + (0.0728P)^2 + 0.0298P], where P = (Fo^2 + 2Fc^2)/3
(Δ/σ)max	<0.0001	<0.0001	<0.0001	0.001
Δρmax, Δρmin (e Å^−3)	0.14, −0.12	0.66, −0.64	0.15, −0.14	0.19, −0.27
Computer programs used: SMART (Bruker, 1998), Kappa-CCD server software (Nonius, 1997), COLLECT (Hooft, 1999), SAINT (Bruker, 2000), DENZO-SMN (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), OSCAIL (McArdle, 2003), PRPKAPPA (Ferguson, 1999).

For polymorphs (I)–(III) the space groups P2₁/c, P2₁/c and P2₁/n were uniquely assigned from the systematic absences. The structures were solved by direct methods and refined with all data on F². A weighting scheme based upon P = [F_o² + 2F_c²]/3 was employed in order to reduce statistical bias (Wilson, 1976). All H atoms were located from difference maps and they were included in the refinements as riding atoms with distances C—H 0.93 Å (aromatic and ethylenic CH), 0.96 Å (CH₃) or 0.97 Å (CH₂) and O—H 0.82 Å at 291 (2) K, and C—H 0.95 Å (aromatic and ethylenic CH), 0.98 Å (CH₃) or 0.99 Å (CH₂) and O—H 0.84 Å at 120 (2) K, and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C,O) for OH and methyl groups.

Supramolecular analyses were made and the diagrams were prepared with the aid of PLATON (Spek, 2003). Details of molecular conformations are given in Table 2 and details of hydrogen-bond dimensions are given in Table 3.¹ Figures 1–9 show the molecular components, with atom-labelling schemes, and aspects of the supramolecular structures.

Table 2
Selected geometrical parameters (Å, °)

				(III)	(III)
	(I)	(IIa)	(IIb)	Mol. 1	Mol. 2
Temperature (K)	291	120	291	120	120
x	Nil	Nil	Nil	1	2
Parameter
Ox3—Nx4	1.417 (2)	1.421 (2)	1.4165 (18)	1.4214 (16)	1.4243 (16)
Nx4—Cx5	1.294 (2)	1.297 (3)	1.291 (2)	1.289 (2)	1.298 (2)
Cx2—Ox3—Nx4	107.08 (17)	108.30 (16)	108.14 (13)	107.10 (12)	107.72 (11)
Ox3—Nx4—Cx5	111.16 (17)	111.37 (17)	111.05 (14)	110.93 (13)	111.00 (12)
Ox1—Cx1—Cx2—Ox3	−177.8 (2)	−168.8 (2)	−168.96 (16)	−173.35 (14)	176.70 (13)
Cx1—Cx2—Ox3—Nx4	−153.1 (2)	−78.8 (2)	−80.63 (18)	−158.92 (13)	145.91 (13)
Cx2—Ox3—Nx4—Cx5	179.5 (2)	173.2 (2)	174.60 (15)	−177.91 (14)	−172.06 (13)
Ox3—Nx4—Cx5—Cx6	1.5 (3)	−1.1 (3)	−1.6 (2)	1.1 (2)	−0.3 (2)
Nx4—Cx5—Cx6—Cx7	171.7 (2)	168.7 (2)	169.29 (17)	172.97 (16)	−170.89 (15)
Nx4—Cx5—Cx11—Cx12	113.3 (2)	124.3 (2)	121.89 (19)	107.38 (19)	−119.08 (16)
Cx6—Cx7—Cx21—Cx22	10.5 (2)	2.4 (4)	2.8 (3)	8.3 (3)	−11.1 (3)
Cx23—Cx24—Ox24—Cx27	175.4 (2)	−179.1 (2)	−178.57 (18)	178.30 (14)	−173.96 (13)

Table 3
Selected hydrogen bond parameters (Å, °)

D—H⋯A	H⋯A	D⋯A	D—H⋯A
(I)
O1—H1⋯O2^i	1.85	2.662 (3)	171
(IIa)
O1—H1⋯O2^i	1.83	2.668 (3)	173
C23—H23⋯N4^ii	2.48	3.409 (3)	166
C22—H22⋯Cg1^ii,†	2.85	3.647 (3)	142
(IIb)
O1—H1⋯O2^i	1.86	2.679 (3)	175
C23—H23⋯N4^ii	2.56	3.472 (2)	167
C22—H22⋯Cg1^ii†	2.94	3.712 (2)	141
(III)
O11—H11⋯O22	1.81	2.6542 (17)	177
O21—H21⋯O12	1.80	2.6410 (17)	178
C215—H215⋯Cg2^iii‡	2.64	3.532 (2)	157
Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) ; (iii) .

†Cg1 is the centroid of the C31–C36 ring.
‡Cg2 is the centroid of the C221–C226 ring.

Figure 1 The molecule in polymorph (I) at 291 K showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2 The molecule in polymorph (II) showing the atom-labelling scheme: (a) at 120 K (IIa) and (b) at 291 K (IIb). Displacement ellipsoids are drawn at the 30% probability level.

Figure 3 The two independent molecules in polymorph (III) at 120 K showing the atom-labelling scheme and the dimeric aggregate formed by the O—H⋯O hydrogen bonds. Displacement ellipsoids are drawn at the 30% probability level.

Figure 4 Part of the crystal structure of polymorph (I) at 291 K showing the formation of a centrosymmetric R2^2(8) dimer. For the sake of clarity, the H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1 - x, 1 - y, 1 - z).

Figure 5 Part of the crystal structure of polymorph (II) at 120 K showing the formation of a centrosymmetric R2^2(8) dimer. For the sake of clarity, the H atoms bonded to C atoms have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1 - x, 1 - y, 1 - z).

Figure 6 Stereoview of part of the crystal structure of polymorph (II) at 120 K showing the formation of a (10) hydrogen-bonded sheet of R2^2(8) and R6^6(52) rings built from O—H⋯O and C—H⋯N hydrogen bonds. For the sake of clarity the H atoms not involved in the motifs shown have been omitted.

Figure 7 Part of the crystal structure of polymorph (II) at 120 K showing the cooperative combination of the C—H⋯N and C—H⋯π(arene) hydrogen bonds. For the sake of clarity the H atoms not involved in the motifs shown have been omitted. The atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions () and (), respectively.

Figure 8 Stereoview of part of the crystal structure of polymorph (III) showing the formation of an [010] chain built of type 2 molecules only.

Figure 9 (a) Projection of part of the crystal structure of polymorph (I) in the domain 0 < y < ½; (b) projection of part of the crystal structure of polymorph (III) in the domain ½ < y < 1.0. For the sake of clarity, the other half of the unit-cell contents has been omitted in each case, as have the H atoms.

2.3. Thermal analysis

DSC measurements were made using a Mettler Toledo model 821e instrument, with heating and cooling at a constant rate of 10 K per minute. The following thermal regime was adopted: samples were cooled from ambient temperature to 153 K and then held for 10 min, heated to 403 K and held for 10 min, cooled to 153 K and held for 10 min, heated to 423 K and held for 10 min, cooled to 153 K and held for 10 min, and finally heated to ambient temperature.

3. Results and discussion

3.1. Crystallization behaviour

An initial dataset collected at 291 (2) K gave a satisfactory solution and refinement for polymorph (I), but at this temperature only 27% of the reflections were labelled as `observed': although these data were 99.1% complete to θ = 32.58%, with an overall data:parameter ratio of 28.4, the ratio of `observed' data to parameters was only 7.5. Accordingly, a second dataset was collected at 120 (2) K using a freshly mounted crystal: this proved to have a different unit cell and a different supramolecular structure from that found from the first data set, and hence this form was denoted as polymorph (II). The observation of different structures derived from diffraction data collected from different crystals at different temperatures immediately raised the question of whether forms (I) and (II) were concomitant polymorphs both present in the original crystalline product, or whether a phase change from (I) to (II) had occurred upon cooling from 291 to 120 K.

Some ten crystals from the original batch were then taken, essentially at random, and their unit-cell dimensions were determined at 291 K: the majority were of polymorph (II) but several of the crystals were of polymorph (I), confirming the occurrence of concomitant polymorphism at ambient temperature. Two further datasets were then collected, one for polymorph (II) at ambient temperature and a second at 120 (2) K for a crystal which had been shown to be of polymorph (I) at ambient temperature: this crystal at 120 K proved to have yet a third unit cell, having undergone a phase transformation upon cooling, and this form is denoted as polymorph (III).

DSC examination of the original mixture of polymorphs showed several distinct events as the temperature was cycled in the range 153–423 K (−120 to +150°C): a reversible phase transition, corresponding to the interconversion of polymorphs (I) and (III), was observed at approximately 173 K, and the melting points of (I) and (II) were observed at 393 and 413 K, respectively. However, while the melting of (I) was reversible, cooling the melt of (II) led to the formation of a glass rather than to crystallization.

3.2. Molecular conformations

In each of the independent molecules in polymorphs (I)–(III) (Figs. 1–3) the intramolecular bond lengths and angles are very similar, and all distances have values which are typical of their types (Allen et al., 1987). However, there are some significant variations in the molecular conformations, as shown by the key torsional angles (Table 2), although the torsional angles in polymorph (II) all show very little variation with temperature. For polymorph (III) the values of those torsional angles which are remote from zero or 180° generally have similar magnitudes for the two independent molecules but with opposite signs, indicating that the two molecules are close to being enantiomorphs and pointing up the pseudosymmetric nature of the hydrogen-bonded dimer (Fig. 3). The most notable variation between the different polymorphs occurs in the torsional angle Cx1—Cx2—Ox3—Nx4, where polymorph (II) adopts quite a different value from those in polymorphs (I) and (III), where the values are, in fact, rather similar in magnitude.

3.3. Supramolecular aggregation

In each polymorph the primary mode of supramolecular aggregation is the formation of R₂²(8) (Bernstein et al., 1995) dimers by means of paired O—H⋯O hydrogen bonds (Table B): these dimers are centrosymmetric in polymorphs (I) and (II) (Figs. 4 and 5) and pseudosymmetric in polymorph (III), where the dimer contains one of each type of independent molecule (Fig. 3). In both (I) and (II) the reference molecule has been selected such that the hydrogen-bonded dimer is centred at (½, ½, ½): in (III) the selected asymmetric unit is approximately centrosymmetric and its centroid lies at approximately (½, ½, 0.22).

In polymorph (II) the dimers are linked into sheets by means of C—H⋯N hydrogen bonds, augmented by C—H⋯π(arene) hydrogen bonds, and the patterns of the hydrogen bonds are same at both 120 and 291 K, while the dimensions change only slightly between these two temperatures (Table 3). The atoms of type C23 in the molecules at (x, y, z) and (1- x, 1 - y, 1 - z) are components of the R₂²(8) dimer centred at (½, ½, ½). These two atoms act as hydrogen-bond donors to the N4 atoms in the molecules at () and (), which lie respectively in the dimers centred at (−½, 1, 0,) and , 0, 1). At the same time the atoms N4 at (x, y, z) and (1 - x, 1 - y, 1 - z) accept hydrogen bonds from the atoms C23 at () and (), which themselves lie in the dimers centred at (−½, 0, 0) and (, 1, 1), respectively. In this manner a (10) sheet is generated (Fig. 6), in which O—H⋯O and C—H⋯N hydrogen bonds generate R₂²(8) and R₆⁶(52) rings, which alternate in chessboard fashion. The C—H⋯π(arene) hydrogen bonds (Table 3) follow exactly the same pattern (Fig. 7) and hence serve to reinforce the sheet generated by the C—H⋯N hydrogen bonds.

By contrast, in polymorph (I) there are no hydrogen bonds between adjacent dimers: in particular, the C—H⋯N and C—H⋯π(arene) hydrogen bonds found in polymorph (II) are both absent from the crystal structure of (I). The only direction-specific interaction of possible significance between the R₂²(8) dimers in (I) is a weak π⋯π stacking interaction. The methoxy-substituted rings C21–C26 in the molecules at (x, y, z) and (-x, 1 - y, 2 - z) are strictly parallel, but both the interplanar spacing, 3.534 (2) Å, and the ring-centroid separation, 3.960 (2) Å, are rather large, associated with a large centroid offset of 1.787 (2) Å; hence, this interaction is probably not structurally significant.

The principal interaction between the dimeric units in polymorph (III) is a C—H⋯π(arene) hydrogen bond which involves only the molecules of type 2 (containing C21 etc.). The aryl C215 atom in the unsubstituted ring of the type 2 molecule at (x, y, z) acts as a hydrogen-bond donor to the substituted ring C221–C216 in the corresponding molecule at (), so forming a chain of type 2 molecules, from which the type 1 molecules are pendent, running parallel to the [010] direction and generated by the 2₁ screw axis along (, y, −¼), see Fig. 8. As in polymorph (I), the π⋯π stacking interactions in (III) again involve the methoxy-substituted rings, in particular those of type 2 molecules at (x, y, z) and (2 - x, 1 - y, -z), see §3.4. Also as in (I), the large interplanar separations and large ring-centroid separations (> 3.8 Å) indicate that these interactions are probably not structurally significant.

3.4. Phase relationship

The relationship between the crystal structures of polymorphs (I) and (III) can readily be understood once it is recognized that the unit cell of (III) can be derived from that of (II) via the transformation (0, 0, 1; 0, −1, 0; 2, 0, 0). In polymorph (I) the dimeric units are centred at (½, ½, ½) and (½, 0, 0), whereas in (III), where the length of the c axis is double that of the a axis in (I), the dimers are located at approximately (½, ½, 0.22), (½, ½, 0.78), (0, 0, 0.28) and (0, 0, 0.72), leading to a very close similarity between the structures of (I) and (III) (Fig. 9). Hence, this temperature-dependent change of structure from P2₁/c with Z′ = 1 at 291 K, to P2₁/n with Z′ = 2 at 120 K can be described as a simple displacive transition. The similarity of molecular conformation between the unique molecules in polymorph (I), and each of the two independent molecules in (III), is entirely consistent with this. In both (I) and (III) the pattern of the hard (Braga et al., 1995) hydrogen bonds is essentially the same and the difference between the supramolecular structures of (I) and (III) depends on a single rather weak C—H⋯π(arene) hydrogen bond in (III), which is absent from the structure of (I).

3.5. Comparison with analogous structures

It is of interest to compare briefly the supramolecular structures of polymorphs (I)–III) with those of the related compounds (IV)–(VI) (Glidewell et al., 2004a,b). In each of (IV)–(VI), the molecules are linked by paired O—H⋯O hydrogen bonds into centrosymmetric dimers, analogous to those observed in (I) and (II), and in both (IV) and (VI) there are no direction-specific interactions between these dimers: in (V), on the other hand, the dimers are weakly linked into chains by a single aromatic π⋯π stacking interaction. It is noteworthy that C—H⋯N hydrogen bonds are absent from the structures of each of (IV)–(VI), in contrast to polymorph (II).

3.6. General comments

In our recent structural studies we have encountered several examples of concomitant polymorphism. Thus, when crystallized from ethanol, 2-iodo-4-nitro aniline yields a mixture of triclinic (P, Z′ = 1) and orthorhombic (Pbca, Z′ = 1) crystals which have slightly different colours (McWilliam et al., 2001); crystallization of ethyl N-(2-amino-6-benzyloxy-5-nitrosopyrimidin-2-yl)-3-aminopropanoate from acetonitrile/ethanol/water (1/1/1 by volume) yields a mixture of two monoclinic polymorphs, one blue (P2₁/c, Z′ = 1) and the other pink (P2₁, Z′ = 2; Quesada et al., 2002), where the conformations of the three independent molecules of the nitrosopyrimidine are all different, so that these concomitant polymorphs are also conformational polymorphs; the 1: 1 adduct formed between (S)-malic acid and 4,4′-bipyridyl crystallizes from methanol as a mixture of triclinic (P1, Z′ = 1) and monoclinic (C2, Z′ = 1) polymorphs (Farrell et al., 2002); benzanilide crystallizes from ethanol in both a monoclinic (C2/c, Z′ = 0.5) form (Kashino et al., 1979) and a triclinic (, Z′ = 1) form (Bowes, Glidewell et al., 2003); the 2:1 adduct formed between triphenylsilanol and 4,4′-bipyridyl forms three triclinic polymorphs (all with Z′ = 0.5, 1 and 4), which crystallize in pairwise-concomitant fashion (Bowes, Ferguson et al., 2003); and crystallization of 1-(6-amino-1,3-benzodioxol-5-yl)-3-(4-methoxyphenyl)prop-2-en-1-one from dimethylform­amide solution gives a mixture of a red monoclinic (P2₁/c, Z′ = 1) polymorph and a yellow triclinic (, Z′ = 2) form, where the two independent molecules in the triclinic form exhibit different conformations, so providing a second example of conformational polymorphism also (Low et al., 2004).

We emphasize that in none of these systems had there been any attempt to engineer such polymorphic behaviour, nor was this behaviour being specifically sought after: instead, each pair of polymorphs was identified serendipitously. In the cases of 2-iodo-4-nitroaniline, the nitrosopyrimidine and the substituted propenone, the identification of the two forms was facilitated by their differences in colour, but in the other examples identification depended solely upon careful scrutiny of the crystalline samples and observation of more than one crystal habit, followed in every case by careful manual separation. Our identification, essentially by chance, of seven such examples within a rather short space of time suggests to us that the phenomenon of concomitant polymorphism may, in fact, be a rather common one, certainly far more common than the current literature (Bernstein et al., 1999) tends to suggest, but one which goes largely un-noticed. On the other hand, we note the recent reports on 3,6,13,16-tetrabromo-2,7,12,17-tetrapropylporphycene, where monoclinic prisms and triclinic plates crystallize concurrently from dichloromethane–hexane (Aritome et al., 2002), and on the 1:1 co-crystal of caffeine and glutaric acid, where monoclinic rods and triclinic blocks crystallize concurrently from chloroform solution (Trask et al., 2004).

4. Concluding remarks

The investigation of the title compound was originally expected to be entirely straightforward, simply providing another example of this class of compound for comparison with the analogues which have been reported recently (Glidewell et al., 2004a,b). In the event, this investigation has proved to be much more complex than those for the previous examples. We emphasize, however, that as with so many examples of polymorphism, and particularly concomitant polymorphism, the structural behaviour can be unravelled, as here, only by careful and painstaking separation of a substantial number of individual crystals followed by their X-ray examination initially at ambient temperature and then at reduced temperature.

Supporting information

S1. Comment

In full text version

S2. Experimental

In full text version

S3. Refinement

In full text version

Computing details

Data collection: SMART (Bruker, 1998) for (I), (IIb); Kappa-CCD server software (Nonius, 1997) for (IIa); COLLECT (Hooft, 1999) for (III). Cell refinement: SAINT (Bruker, 2000) for (I), (IIb); DENZO-SMN (Otwinowski & Minor, 1997) for (IIa); DENZO (Otwinowski & Minor, 1997) & COLLECT for (III). Data reduction: SAINT (Bruker, 2000) for (I), (IIb); DENZO-SMN for (IIa); DENZO & COLLECT for (III). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (I), (IIb); OSCAIL (McArdle , 2003) and SHELXS97 (Sheldrick, 1997) for (IIa); OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997) for (III). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (I), (IIb); OSCAIL and SHELXS97 (Sheldrick, 1997) for (IIa); OSCAIL and SHELXL97 (Sheldrick, 1997) for (III). For all compounds, molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

In full text version

(I) (E)-[1-(4-methoxyphenyl)-3-phenyl-2-propenylideneamino)oxyacetic acid

Crystal data

C18H17NO4	F(000) = 656
Mr = 311.33	Dx = 1.254 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5963 reflections
a = 8.5153 (7) Å	θ = 2.1–32.6°
b = 16.0591 (13) Å	µ = 0.09 mm^−1
c = 12.1476 (10) Å	T = 291 K
β = 96.801 (2)°	Plate, colourless
V = 1649.5 (2) Å^3	0.45 × 0.40 × 0.04 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area detector diffractometer	5963 independent reflections
Radiation source: fine-focus sealed X-ray tube	1586 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ϕ–ω scans	θmax = 32.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS, Bruker, 2000)	h = −12→12
Tmin = 0.952, Tmax = 0.996	k = −16→24
16995 measured reflections	l = −17→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.172	H-atom parameters constrained
S = 0.86	w = 1/[σ^2(Fo^2) + (0.0654P)^2] where P = (Fo^2 + 2Fc^2)/3
5963 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.14 e Å^−3
0 restraints	Δρmin = −0.12 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2993 (4)	0.44487 (15)	0.4914 (2)	0.0959 (8)
O2	0.3503 (2)	0.48398 (12)	0.57345 (16)	0.1263 (7)
O1	0.3735 (2)	0.43644 (12)	0.40495 (14)	0.1201 (7)
C11	−0.2197 (2)	0.28337 (14)	0.68035 (19)	0.0706 (6)
C12	−0.1911 (3)	0.22962 (15)	0.7691 (2)	0.0888 (7)
C13	−0.2876 (4)	0.16258 (18)	0.7787 (3)	0.1155 (10)
C14	−0.4145 (4)	0.1500 (2)	0.7009 (4)	0.1423 (16)
C15	−0.4436 (4)	0.2016 (3)	0.6141 (3)	0.1511 (17)
C16	−0.3468 (3)	0.2687 (2)	0.6026 (2)	0.1085 (9)
C2	0.1439 (4)	0.40161 (15)	0.4777 (2)	0.1028 (8)
O3	0.0657 (2)	0.41549 (9)	0.57237 (13)	0.1006 (5)
N4	−0.0365 (2)	0.34680 (10)	0.58148 (15)	0.0791 (5)
C5	−0.1124 (2)	0.35421 (13)	0.66720 (17)	0.0684 (6)
C6	−0.0998 (2)	0.42388 (12)	0.74340 (16)	0.0696 (6)
C7	−0.1928 (2)	0.43479 (13)	0.82325 (17)	0.0705 (6)
C21	−0.1906 (2)	0.50399 (12)	0.90073 (16)	0.0610 (5)
C23	−0.1080 (2)	0.64037 (13)	0.96543 (17)	0.0683 (6)
C22	−0.1050 (2)	0.57650 (12)	0.89120 (16)	0.0666 (6)
C24	−0.1972 (2)	0.63359 (12)	1.05257 (16)	0.0613 (5)
O24	−0.19435 (16)	0.70151 (9)	1.12107 (12)	0.0796 (4)
C27	−0.2930 (3)	0.70124 (16)	1.20787 (19)	0.0992 (8)
C25	−0.2818 (2)	0.56231 (13)	1.06569 (18)	0.0721 (6)
C26	−0.2783 (2)	0.49899 (13)	0.98954 (18)	0.0729 (6)
H1	0.4532	0.4656	0.4119	0.180*
H12	−0.1056	0.2390	0.8227	0.107*
H13	−0.2668	0.1259	0.8379	0.139*
H4	−0.4816	0.1051	0.7081	0.171*
H15	−0.5299	0.1919	0.5613	0.181*
H16	−0.3676	0.3042	0.5421	0.130*
H2A	0.0797	0.4225	0.4122	0.123*
H2B	0.1597	0.3424	0.4680	0.123*
H6	−0.0220	0.4635	0.7363	0.084*
H7	−0.2676	0.3935	0.8302	0.085*
H23	−0.0497	0.6885	0.9571	0.082*
H22	−0.0441	0.5819	0.8329	0.080*
H27A	−0.4013	0.6943	1.1769	0.149*
H27B	−0.2815	0.7531	1.2474	0.149*
H27C	−0.2629	0.6562	1.2578	0.149*
H25	−0.3407	0.5568	1.1251	0.087*
H26	−0.3371	0.4511	0.9981	0.087*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.154 (3)	0.0612 (15)	0.0794 (18)	−0.0045 (17)	0.0413 (18)	−0.0039 (13)
O2	0.1767 (19)	0.1113 (14)	0.0998 (13)	−0.0377 (14)	0.0530 (13)	−0.0317 (12)
O1	0.1646 (19)	0.1167 (16)	0.0876 (12)	−0.0190 (13)	0.0505 (13)	−0.0161 (10)
C11	0.0610 (13)	0.0748 (15)	0.0766 (14)	−0.0006 (12)	0.0109 (12)	−0.0239 (13)
C12	0.0845 (16)	0.0757 (16)	0.1051 (19)	−0.0129 (14)	0.0068 (14)	−0.0041 (15)
C13	0.121 (2)	0.0910 (19)	0.143 (3)	−0.0400 (19)	0.050 (2)	−0.0258 (18)
C14	0.121 (3)	0.168 (4)	0.154 (3)	−0.080 (3)	0.081 (3)	−0.097 (3)
C15	0.091 (2)	0.246 (5)	0.119 (3)	−0.059 (3)	0.025 (2)	−0.086 (3)
C16	0.0780 (16)	0.159 (3)	0.0866 (18)	−0.0092 (19)	0.0005 (15)	−0.0386 (18)
C2	0.163 (3)	0.0716 (15)	0.0811 (17)	−0.0123 (18)	0.0438 (18)	−0.0030 (13)
O3	0.1629 (15)	0.0579 (9)	0.0892 (11)	−0.0131 (10)	0.0492 (11)	−0.0078 (8)
N4	0.1055 (13)	0.0529 (10)	0.0786 (12)	−0.0007 (10)	0.0104 (11)	−0.0023 (9)
C5	0.0762 (14)	0.0636 (14)	0.0628 (13)	0.0180 (12)	−0.0024 (11)	−0.0071 (11)
C6	0.0769 (14)	0.0583 (13)	0.0721 (14)	0.0057 (11)	0.0028 (12)	0.0000 (10)
C7	0.0647 (12)	0.0629 (13)	0.0816 (14)	0.0025 (11)	−0.0007 (12)	−0.0059 (11)
C21	0.0567 (11)	0.0550 (12)	0.0698 (13)	0.0058 (10)	0.0016 (10)	−0.0019 (10)
C23	0.0764 (14)	0.0548 (12)	0.0745 (14)	−0.0010 (11)	0.0127 (12)	0.0027 (10)
C22	0.0769 (14)	0.0595 (13)	0.0657 (13)	0.0054 (11)	0.0183 (11)	0.0032 (10)
C24	0.0586 (12)	0.0569 (13)	0.0667 (13)	0.0068 (10)	0.0004 (10)	−0.0061 (10)
O24	0.0857 (10)	0.0726 (10)	0.0822 (10)	0.0011 (8)	0.0168 (8)	−0.0168 (8)
C27	0.1024 (17)	0.110 (2)	0.0886 (17)	0.0071 (16)	0.0270 (15)	−0.0283 (14)
C25	0.0641 (12)	0.0710 (14)	0.0846 (15)	−0.0009 (11)	0.0226 (11)	−0.0079 (12)
C26	0.0624 (12)	0.0629 (13)	0.0955 (16)	−0.0076 (11)	0.0180 (12)	−0.0075 (12)

Geometric parameters (Å, º)

C1—O2	1.214 (3)	C5—C6	1.448 (3)
C1—O1	1.295 (3)	C6—C7	1.335 (3)
C1—C2	1.486 (4)	C6—H6	0.93
O1—H1	0.82	C7—C21	1.455 (3)
C11—C16	1.370 (3)	C7—H7	0.93
C11—C12	1.380 (3)	C21—C26	1.385 (3)
C11—C5	1.479 (3)	C21—C22	1.386 (3)
C12—C13	1.368 (3)	C23—C22	1.368 (3)
C12—H12	0.93	C23—C24	1.378 (3)
C13—C14	1.364 (4)	C23—H23	0.93
C13—H13	0.93	C22—H22	0.93
C14—C15	1.341 (5)	C24—O24	1.370 (2)
C14—H4	0.93	C24—C25	1.372 (3)
C15—C16	1.374 (5)	O24—C27	1.424 (2)
C15—H15	0.93	C27—H27A	0.96
C16—H16	0.93	C27—H27B	0.96
C2—O3	1.414 (3)	C27—H27C	0.96
C2—H2A	0.97	C25—C26	1.377 (3)
C2—H2B	0.97	C25—H25	0.93
O3—N4	1.417 (2)	C26—H26	0.93
N4—C5	1.294 (2)
O2—C1—O1	123.9 (3)	C6—C5—C11	121.7 (2)
O2—C1—C2	124.2 (2)	C7—C6—C5	124.1 (2)
O1—C1—C2	111.9 (2)	C7—C6—H6	118.0
C1—O1—H1	109.5	C5—C6—H6	118.0
C16—C11—C12	118.9 (2)	C6—C7—C21	127.4 (2)
C16—C11—C5	120.3 (2)	C6—C7—H7	116.3
C12—C11—C5	120.7 (2)	C21—C7—H7	116.3
C13—C12—C11	120.5 (3)	C26—C21—C22	116.82 (18)
C13—C12—H12	119.8	C26—C21—C7	119.51 (19)
C11—C12—H12	119.8	C22—C21—C7	123.67 (19)
C14—C13—C12	119.5 (3)	C22—C23—C24	120.1 (2)
C14—C13—H13	120.3	C22—C23—H23	119.9
C12—C13—H13	120.3	C24—C23—H23	119.9
C15—C14—C13	120.7 (3)	C23—C22—C21	121.60 (19)
C15—C14—H4	119.6	C23—C22—H22	119.2
C13—C14—H4	119.6	C21—C22—H22	119.2
C14—C15—C16	120.5 (3)	O24—C24—C25	124.42 (19)
C14—C15—H15	119.7	O24—C24—C23	115.57 (19)
C16—C15—H15	119.7	C25—C24—C23	120.01 (19)
C11—C16—C15	119.9 (3)	C24—O24—C27	118.53 (17)
C11—C16—H16	120.1	O24—C27—H27A	109.5
C15—C16—H16	120.1	O24—C27—H27B	109.5
O3—C2—C1	109.5 (2)	H27A—C27—H27B	109.5
O3—C2—H2A	109.8	O24—C27—H27C	109.5
C1—C2—H2A	109.8	H27A—C27—H27C	109.5
O3—C2—H2B	109.8	H27B—C27—H27C	109.5
C1—C2—H2B	109.8	C24—C25—C26	118.97 (19)
H2A—C2—H2B	108.2	C24—C25—H25	120.5
C2—O3—N4	107.08 (17)	C26—C25—H25	120.5
C5—N4—O3	111.16 (17)	C25—C26—C21	122.5 (2)
N4—C5—C6	125.4 (2)	C25—C26—H26	118.8
N4—C5—C11	112.94 (18)	C21—C26—H26	118.8
C16—C11—C12—C13	0.4 (3)	N4—C5—C6—C7	171.67 (19)
C5—C11—C12—C13	−177.7 (2)	C11—C5—C6—C7	−7.2 (3)
C11—C12—C13—C14	−1.2 (4)	C5—C6—C7—C21	−178.12 (18)
C12—C13—C14—C15	1.4 (5)	C6—C7—C21—C26	−169.78 (19)
C13—C14—C15—C16	−0.7 (6)	C6—C7—C21—C22	10.5 (3)
C12—C11—C16—C15	0.3 (4)	C24—C23—C22—C21	0.2 (3)
C5—C11—C16—C15	178.4 (2)	C26—C21—C22—C23	−0.5 (3)
C14—C15—C16—C11	−0.2 (5)	C7—C21—C22—C23	179.23 (18)
O2—C1—C2—O3	1.7 (4)	C22—C23—C24—O24	−178.90 (17)
O1—C1—C2—O3	−177.8 (2)	C22—C23—C24—C25	0.7 (3)
C1—C2—O3—N4	−153.09 (19)	C25—C24—O24—C27	−4.2 (3)
C2—O3—N4—C5	179.48 (19)	C23—C24—O24—C27	175.38 (17)
O3—N4—C5—C6	1.5 (3)	O24—C24—C25—C26	178.34 (18)
O3—N4—C5—C11	−179.55 (17)	C23—C24—C25—C26	−1.2 (3)
C16—C11—C5—N4	−64.8 (2)	C24—C25—C26—C21	0.9 (3)
C12—C11—C5—N4	113.3 (2)	C22—C21—C26—C25	−0.1 (3)
C16—C11—C5—C6	114.2 (2)	C7—C21—C26—C25	−179.80 (19)
C12—C11—C5—C6	−67.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	1.85	2.662 (3)	171

Symmetry code: (i) −x+1, −y+1, −z+1.

(IIa) (E)-[1-(4-methoxyphenyl)-3-phenyl-2-propenylideneamino)oxyacetic acid

Crystal data

C18H17NO4	F(000) = 656
Mr = 311.33	Dx = 1.288 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3690 reflections
a = 6.4499 (2) Å	θ = 3.0–27.5°
b = 14.9693 (5) Å	µ = 0.09 mm^−1
c = 16.6559 (6) Å	T = 120 K
β = 92.947 (2)°	Plate, yellow
V = 1606.01 (9) Å^3	0.25 × 0.20 × 0.05 mm
Z = 4

Data collection

Kappa-CCD diffractometer	3690 independent reflections
Radiation source: fine-focus sealed X-ray tube	2647 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan SORTAV (Blessing 1995 and 1997	h = −8→8
Tmin = 0.967, Tmax = 0.995	k = −19→19
17758 measured reflections	l = −21→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.232	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.1318P)^2 + 0.4171P] where P = (Fo^2 + 2Fc^2)/3
3690 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.66 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5113 (3)	0.56573 (15)	0.40172 (15)	0.0304 (5)
O2	0.3533 (2)	0.52726 (11)	0.41955 (11)	0.0350 (4)
O1	0.6769 (2)	0.57544 (12)	0.45065 (11)	0.0352 (4)
C11	0.0796 (4)	0.43697 (15)	0.16447 (15)	0.0311 (5)
C12	−0.1059 (4)	0.39619 (16)	0.18352 (17)	0.0367 (6)
C13	−0.1517 (4)	0.30945 (16)	0.15832 (19)	0.0433 (7)
C14	−0.0143 (5)	0.26405 (18)	0.11227 (17)	0.0482 (8)
C15	0.1672 (5)	0.30496 (18)	0.09115 (17)	0.0467 (7)
C16	0.2164 (4)	0.39095 (17)	0.11727 (17)	0.0401 (6)
C2	0.5414 (4)	0.60708 (16)	0.32101 (16)	0.0336 (6)
O3	0.3571 (2)	0.61316 (10)	0.27205 (11)	0.0336 (4)
N4	0.3144 (3)	0.52776 (12)	0.23787 (13)	0.0310 (5)
C5	0.1352 (4)	0.52637 (15)	0.19887 (15)	0.0296 (5)
C6	−0.0067 (4)	0.60192 (15)	0.19205 (15)	0.0299 (5)
C7	−0.1762 (4)	0.60633 (15)	0.14176 (15)	0.0302 (5)
C21	−0.3231 (3)	0.68066 (15)	0.13578 (14)	0.0287 (5)
C26	−0.4999 (4)	0.67479 (15)	0.08457 (15)	0.0321 (6)
C25	−0.6458 (4)	0.74346 (16)	0.07875 (15)	0.0338 (6)
C24	−0.6148 (4)	0.81959 (15)	0.12510 (15)	0.0301 (5)
O24	−0.7452 (3)	0.89141 (11)	0.12568 (11)	0.0390 (5)
C27	−0.9303 (4)	0.88886 (19)	0.07543 (18)	0.0414 (7)
C23	−0.4387 (4)	0.82659 (15)	0.17666 (16)	0.0334 (6)
C22	−0.2960 (4)	0.75869 (15)	0.18168 (15)	0.0308 (5)
H1	0.6613	0.5462	0.4930	0.053*
H12	−0.2021	0.4280	0.2141	0.044*
H13	−0.2768	0.2816	0.1727	0.052*
H14	−0.0445	0.2047	0.0951	0.058*
H15	0.2595	0.2739	0.0584	0.056*
H16	0.3424	0.4182	0.1030	0.048*
H2A	0.5998	0.6678	0.3291	0.040*
H2B	0.6438	0.5712	0.2927	0.040*
H6	0.0228	0.6520	0.2258	0.036*
H7	−0.2029	0.5568	0.1071	0.036*
H26	−0.5218	0.6226	0.0528	0.039*
H25	−0.7653	0.7381	0.0433	0.041*
H27A	−0.8948	0.8910	0.0190	0.062*
H27B	−1.0175	0.9403	0.0873	0.062*
H27C	−1.0061	0.8336	0.0854	0.062*
H23	−0.4172	0.8787	0.2085	0.040*
H22	−0.1763	0.7646	0.2170	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0269 (12)	0.0258 (11)	0.0385 (13)	−0.0020 (9)	0.0018 (10)	−0.0055 (10)
O2	0.0291 (9)	0.0370 (9)	0.0390 (10)	−0.0087 (7)	0.0025 (7)	0.0009 (7)
O1	0.0320 (9)	0.0357 (9)	0.0376 (10)	−0.0111 (7)	−0.0011 (8)	0.0036 (7)
C11	0.0369 (13)	0.0226 (11)	0.0333 (13)	0.0046 (9)	−0.0044 (10)	0.0009 (9)
C12	0.0401 (14)	0.0270 (12)	0.0426 (15)	0.0026 (10)	−0.0030 (11)	−0.0020 (10)
C13	0.0466 (15)	0.0257 (12)	0.0562 (17)	−0.0023 (10)	−0.0123 (13)	0.0013 (11)
C14	0.069 (2)	0.0279 (13)	0.0452 (17)	0.0049 (12)	−0.0194 (15)	−0.0036 (11)
C15	0.0655 (19)	0.0372 (14)	0.0370 (15)	0.0181 (13)	−0.0011 (14)	−0.0049 (12)
C16	0.0479 (15)	0.0331 (13)	0.0391 (15)	0.0077 (11)	0.0017 (12)	0.0027 (11)
C2	0.0274 (12)	0.0300 (12)	0.0432 (15)	−0.0047 (9)	−0.0004 (11)	0.0041 (10)
O3	0.0323 (9)	0.0234 (8)	0.0444 (10)	−0.0015 (6)	−0.0036 (8)	0.0013 (7)
N4	0.0330 (11)	0.0235 (9)	0.0365 (11)	−0.0014 (8)	0.0027 (9)	0.0019 (8)
C5	0.0300 (12)	0.0258 (11)	0.0331 (12)	−0.0001 (9)	0.0038 (10)	0.0030 (9)
C6	0.0313 (12)	0.0235 (11)	0.0351 (13)	−0.0002 (9)	0.0038 (10)	0.0014 (9)
C7	0.0331 (12)	0.0239 (11)	0.0336 (13)	−0.0014 (9)	0.0026 (10)	0.0007 (9)
C21	0.0302 (12)	0.0242 (11)	0.0317 (12)	0.0008 (9)	0.0009 (10)	0.0032 (9)
C26	0.0372 (13)	0.0267 (11)	0.0321 (13)	−0.0016 (9)	−0.0009 (10)	−0.0019 (10)
C25	0.0299 (12)	0.0336 (12)	0.0372 (14)	0.0001 (10)	−0.0048 (10)	0.0023 (10)
C24	0.0283 (12)	0.0260 (11)	0.0360 (13)	0.0011 (9)	0.0022 (10)	0.0051 (10)
O24	0.0338 (9)	0.0365 (10)	0.0458 (11)	0.0103 (7)	−0.0056 (8)	−0.0009 (8)
C27	0.0268 (12)	0.0449 (15)	0.0523 (17)	0.0075 (10)	−0.0009 (11)	0.0024 (12)
C23	0.0369 (13)	0.0247 (11)	0.0381 (14)	−0.0015 (9)	−0.0033 (11)	0.0000 (10)
C22	0.0297 (12)	0.0262 (11)	0.0360 (13)	−0.0005 (9)	−0.0043 (10)	0.0035 (10)

Geometric parameters (Å, º)

C1—O2	1.221 (3)	C5—C6	1.456 (3)
C1—O1	1.318 (3)	C6—C7	1.344 (3)
C1—C2	1.501 (4)	C6—H6	0.95
O1—H1	0.84	C7—C21	1.461 (3)
C11—C16	1.394 (4)	C7—H7	0.95
C11—C12	1.394 (3)	C21—C26	1.391 (3)
C11—C5	1.492 (3)	C21—C22	1.402 (3)
C12—C13	1.392 (3)	C26—C25	1.393 (3)
C12—H12	0.95	C26—H26	0.95
C13—C14	1.380 (4)	C25—C24	1.385 (3)
C13—H13	0.95	C25—H25	0.95
C14—C15	1.383 (4)	C24—O24	1.365 (3)
C14—H14	0.95	C24—C23	1.393 (3)
C15—C16	1.390 (4)	O24—C27	1.423 (3)
C15—H15	0.95	C27—H27A	0.98
C16—H16	0.95	C27—H27B	0.98
C2—O3	1.409 (3)	C27—H27C	0.98
C2—H2A	0.99	C23—C22	1.371 (3)
C2—H2B	0.99	C23—H23	0.95
O3—N4	1.421 (2)	C22—H22	0.95
N4—C5	1.297 (3)
O2—C1—O1	124.2 (2)	C6—C5—C11	121.9 (2)
O2—C1—C2	124.1 (2)	C7—C6—C5	125.1 (2)
O1—C1—C2	111.76 (19)	C7—C6—H6	117.5
C1—O1—H1	109.5	C5—C6—H6	117.5
C16—C11—C12	119.2 (2)	C6—C7—C21	125.7 (2)
C16—C11—C5	120.9 (2)	C6—C7—H7	117.2
C12—C11—C5	119.8 (2)	C21—C7—H7	117.2
C13—C12—C11	120.7 (3)	C26—C21—C22	117.5 (2)
C13—C12—H12	119.6	C26—C21—C7	120.1 (2)
C11—C12—H12	119.6	C22—C21—C7	122.4 (2)
C14—C13—C12	119.7 (3)	C21—C26—C25	121.7 (2)
C14—C13—H13	120.2	C21—C26—H26	119.2
C12—C13—H13	120.2	C25—C26—H26	119.2
C13—C14—C15	120.0 (3)	C24—C25—C26	119.4 (2)
C13—C14—H14	120.0	C24—C25—H25	120.3
C15—C14—H14	120.0	C26—C25—H25	120.3
C14—C15—C16	120.9 (3)	O24—C24—C25	125.5 (2)
C14—C15—H15	119.6	O24—C24—C23	114.8 (2)
C16—C15—H15	119.6	C25—C24—C23	119.7 (2)
C15—C16—C11	119.6 (3)	C24—O24—C27	118.25 (19)
C15—C16—H16	120.2	O24—C27—H27A	109.5
C11—C16—H16	120.2	O24—C27—H27B	109.5
O3—C2—C1	113.64 (19)	H27A—C27—H27B	109.5
O3—C2—H2A	108.8	O24—C27—H27C	109.5
C1—C2—H2A	108.8	H27A—C27—H27C	109.5
O3—C2—H2B	108.8	H27B—C27—H27C	109.5
C1—C2—H2B	108.8	C22—C23—C24	120.4 (2)
H2A—C2—H2B	107.7	C22—C23—H23	119.8
C2—O3—N4	108.30 (16)	C24—C23—H23	119.8
C5—N4—O3	111.37 (17)	C23—C22—C21	121.3 (2)
N4—C5—C6	124.6 (2)	C23—C22—H22	119.3
N4—C5—C11	113.41 (19)	C21—C22—H22	119.3
C16—C11—C12—C13	2.2 (4)	N4—C5—C6—C7	168.7 (2)
C5—C11—C12—C13	−173.9 (2)	C11—C5—C6—C7	−14.9 (4)
C11—C12—C13—C14	−1.6 (4)	C5—C6—C7—C21	178.3 (2)
C12—C13—C14—C15	−0.3 (4)	C6—C7—C21—C26	−176.1 (2)
C13—C14—C15—C16	1.5 (4)	C6—C7—C21—C22	2.4 (4)
C14—C15—C16—C11	−0.9 (4)	C22—C21—C26—C25	−0.1 (3)
C12—C11—C16—C15	−1.0 (4)	C7—C21—C26—C25	178.5 (2)
C5—C11—C16—C15	175.1 (2)	C21—C26—C25—C24	−0.1 (4)
O2—C1—C2—O3	11.7 (3)	C26—C25—C24—O24	−179.6 (2)
O1—C1—C2—O3	−168.81 (19)	C26—C25—C24—C23	0.1 (4)
C1—C2—O3—N4	−78.8 (2)	C25—C24—O24—C27	0.6 (4)
C2—O3—N4—C5	173.23 (19)	C23—C24—O24—C27	−179.1 (2)
O3—N4—C5—C6	−1.1 (3)	O24—C24—C23—C22	179.8 (2)
O3—N4—C5—C11	−177.76 (18)	C25—C24—C23—C22	0.1 (4)
C16—C11—C5—N4	−51.8 (3)	C24—C23—C22—C21	−0.3 (4)
C12—C11—C5—N4	124.3 (2)	C26—C21—C22—C23	0.3 (4)
C16—C11—C5—C6	131.5 (3)	C7—C21—C22—C23	−178.2 (2)
C12—C11—C5—C6	−52.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.84	1.83	2.668 (2)	174
C23—H23···N4^ii	0.95	2.48	3.409 (3)	166
C22—H22···Cg1^ii	0.95	2.85	3.647 (3)	142

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+1/2.

(IIb) (E)-[1-(4-methoxyphenyl)-3-phenyl-2-propenylideneamino)oxyacetic acid

Crystal data

C18H17NO4	F(000) = 656
Mr = 311.33	Dx = 1.248 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3837 reflections
a = 6.4238 (3) Å	θ = 1.8–27.6°
b = 15.1513 (9) Å	µ = 0.09 mm^−1
c = 17.0552 (9) Å	T = 291 K
β = 93.167 (2)°	Plate, colourless
V = 1657.43 (15) Å^3	0.25 × 0.20 × 0.05 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area detector diffractometer	3837 independent reflections
Radiation source: fine-focus sealed X-ray tube	2171 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ϕ–ω scans	θmax = 27.6°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→8
Tmin = 0.982, Tmax = 0.996	k = −19→19
13953 measured reflections	l = −22→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.151	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0795P)^2 + 0.0527P] where P = (Fo^2 + 2Fc^2)/3
3837 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.14 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.6749 (2)	0.57149 (10)	0.44883 (8)	0.0731 (4)
O2	0.35075 (19)	0.52460 (10)	0.42022 (8)	0.0715 (4)
O3	0.35183 (19)	0.60586 (8)	0.27465 (8)	0.0655 (4)
O24	−0.7423 (2)	0.88371 (10)	0.12369 (9)	0.0827 (5)
N4	0.3106 (2)	0.52168 (9)	0.24115 (9)	0.0589 (4)
C1	0.5087 (3)	0.56167 (12)	0.40199 (11)	0.0576 (5)
C2	0.5374 (3)	0.60012 (13)	0.32253 (12)	0.0638 (5)
C5	0.1331 (3)	0.52079 (11)	0.20183 (10)	0.0549 (4)
C6	−0.0105 (3)	0.59500 (11)	0.19403 (11)	0.0575 (4)
C7	−0.1774 (3)	0.59977 (12)	0.14494 (11)	0.0576 (4)
C11	0.0793 (3)	0.43272 (12)	0.16713 (11)	0.0595 (5)
C12	−0.1032 (3)	0.39073 (13)	0.18608 (13)	0.0733 (6)
C13	−0.1463 (4)	0.30646 (15)	0.15944 (16)	0.0896 (7)
C14	−0.0131 (5)	0.26365 (17)	0.11396 (15)	0.0972 (9)
C15	0.1652 (5)	0.30432 (17)	0.09294 (14)	0.0970 (8)
C16	0.2143 (4)	0.38905 (14)	0.12045 (13)	0.0788 (6)
C21	−0.3237 (3)	0.67349 (11)	0.13728 (10)	0.0536 (4)
C22	−0.2960 (3)	0.75123 (12)	0.18074 (11)	0.0622 (5)
C23	−0.4369 (3)	0.81881 (12)	0.17438 (12)	0.0670 (5)
C24	−0.6123 (3)	0.81232 (13)	0.12425 (11)	0.0614 (5)
C27	−0.9292 (3)	0.88148 (17)	0.07492 (15)	0.0883 (7)
C25	−0.6452 (3)	0.73650 (14)	0.08002 (12)	0.0674 (5)
C26	−0.4998 (3)	0.66828 (13)	0.08728 (11)	0.0651 (5)
H1	0.6609	0.5435	0.4894	0.110*
H2A	0.5964	0.6588	0.3289	0.077*
H2B	0.6368	0.5642	0.2960	0.077*
H12	−0.1969	0.4196	0.2169	0.088*
H13	−0.2684	0.2787	0.1729	0.108*
H14	−0.0430	0.2065	0.0970	0.117*
H15	0.2542	0.2755	0.0602	0.116*
H16	0.3378	0.4159	0.1073	0.095*
H6	0.0175	0.6434	0.2264	0.069*
H7	−0.2040	0.5515	0.1122	0.069*
H22	−0.1788	0.7571	0.2148	0.075*
H23	−0.4143	0.8697	0.2042	0.080*
H27A	−0.8953	0.8811	0.0208	0.132*
H27B	−1.0118	0.9326	0.0850	0.132*
H27C	−1.0066	0.8292	0.0861	0.132*
H25	−0.7626	0.7312	0.0459	0.081*
H26	−0.5223	0.6175	0.0574	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0626 (8)	0.0832 (10)	0.0719 (9)	−0.0270 (7)	−0.0102 (7)	0.0086 (7)
O2	0.0558 (7)	0.0877 (10)	0.0707 (8)	−0.0206 (7)	0.0021 (6)	0.0051 (7)
O3	0.0661 (8)	0.0492 (7)	0.0792 (9)	−0.0051 (6)	−0.0124 (7)	0.0042 (6)
O24	0.0735 (9)	0.0773 (9)	0.0947 (11)	0.0247 (7)	−0.0188 (8)	−0.0045 (8)
N4	0.0633 (9)	0.0475 (9)	0.0652 (9)	−0.0029 (7)	−0.0026 (8)	0.0031 (7)
C1	0.0509 (10)	0.0543 (10)	0.0673 (11)	−0.0077 (8)	0.0001 (9)	−0.0052 (9)
C2	0.0553 (11)	0.0610 (11)	0.0741 (12)	−0.0123 (9)	−0.0054 (9)	0.0066 (9)
C5	0.0591 (10)	0.0500 (10)	0.0554 (10)	−0.0005 (8)	0.0011 (8)	0.0051 (8)
C6	0.0597 (11)	0.0465 (10)	0.0657 (11)	−0.0001 (8)	−0.0015 (9)	−0.0004 (8)
C7	0.0629 (11)	0.0502 (10)	0.0589 (10)	−0.0008 (8)	−0.0034 (9)	0.0015 (8)
C11	0.0668 (12)	0.0497 (10)	0.0606 (11)	0.0073 (9)	−0.0095 (9)	0.0021 (8)
C12	0.0744 (13)	0.0556 (11)	0.0889 (15)	−0.0018 (10)	−0.0042 (11)	−0.0004 (10)
C13	0.0964 (16)	0.0584 (13)	0.1106 (18)	−0.0066 (12)	−0.0255 (15)	−0.0016 (13)
C14	0.135 (2)	0.0598 (14)	0.0920 (17)	0.0059 (15)	−0.0358 (18)	−0.0120 (12)
C15	0.139 (2)	0.0751 (16)	0.0759 (15)	0.0344 (16)	−0.0012 (16)	−0.0107 (12)
C16	0.0901 (15)	0.0689 (13)	0.0777 (14)	0.0156 (11)	0.0079 (12)	−0.0018 (11)
C21	0.0541 (10)	0.0501 (10)	0.0558 (10)	−0.0033 (8)	−0.0043 (8)	0.0057 (8)
C22	0.0577 (10)	0.0536 (10)	0.0727 (12)	−0.0011 (9)	−0.0185 (9)	0.0021 (9)
C23	0.0678 (12)	0.0513 (10)	0.0796 (13)	0.0017 (9)	−0.0170 (11)	−0.0053 (9)
C24	0.0566 (10)	0.0607 (11)	0.0659 (11)	0.0043 (9)	−0.0055 (9)	0.0057 (9)
C27	0.0576 (12)	0.0967 (17)	0.1090 (18)	0.0169 (11)	−0.0097 (12)	0.0088 (14)
C25	0.0588 (11)	0.0716 (13)	0.0695 (12)	−0.0012 (10)	−0.0165 (9)	0.0045 (10)
C26	0.0712 (12)	0.0582 (11)	0.0643 (11)	−0.0027 (9)	−0.0114 (10)	−0.0035 (9)

Geometric parameters (Å, º)

C1—O2	1.215 (2)	C16—H16	0.93
C1—O1	1.306 (2)	C6—C7	1.326 (2)
C1—C2	1.496 (3)	C6—H6	0.93
O1—H1	0.82	C7—C21	1.461 (2)
C2—O3	1.410 (2)	C7—H7	0.93
C2—H2A	0.97	C21—C26	1.381 (2)
C2—H2B	0.97	C21—C22	1.398 (2)
O3—N4	1.4165 (18)	C22—C23	1.367 (2)
N4—C5	1.291 (2)	C22—H22	0.93
C5—C6	1.456 (2)	C23—C24	1.380 (2)
C5—C11	1.493 (2)	C23—H23	0.93
C11—C16	1.379 (3)	C24—O24	1.366 (2)
C11—C12	1.387 (3)	C24—C25	1.384 (3)
C12—C13	1.378 (3)	O24—C27	1.423 (2)
C12—H12	0.93	C27—H27A	0.96
C13—C14	1.352 (4)	C27—H27B	0.96
C13—H13	0.93	C27—H27C	0.96
C14—C15	1.366 (4)	C25—C26	1.394 (3)
C14—H14	0.93	C25—H25	0.93
C15—C16	1.397 (3)	C26—H26	0.93
C15—H15	0.93
O2—C1—O1	124.19 (17)	C15—C16—H16	120.1
O2—C1—C2	123.94 (16)	C7—C6—C5	125.89 (17)
O1—C1—C2	111.86 (15)	C7—C6—H6	117.1
C1—O1—H1	109.5	C5—C6—H6	117.1
O3—C2—C1	113.97 (15)	C6—C7—C21	126.31 (17)
O3—C2—H2A	108.8	C6—C7—H7	116.8
C1—C2—H2A	108.8	C21—C7—H7	116.8
O3—C2—H2B	108.8	C26—C21—C22	116.85 (16)
C1—C2—H2B	108.8	C26—C21—C7	120.83 (16)
H2A—C2—H2B	107.7	C22—C21—C7	122.31 (15)
C2—O3—N4	108.14 (13)	C23—C22—C21	121.65 (16)
C5—N4—O3	111.05 (14)	C23—C22—H22	119.2
N4—C5—C6	125.21 (16)	C21—C22—H22	119.2
N4—C5—C11	113.21 (15)	C22—C23—C24	120.68 (17)
C6—C5—C11	121.50 (16)	C22—C23—H23	119.7
C16—C11—C12	118.76 (19)	C24—C23—H23	119.7
C16—C11—C5	121.23 (19)	O24—C24—C23	115.22 (17)
C12—C11—C5	119.86 (18)	O24—C24—C25	125.32 (17)
C13—C12—C11	120.3 (2)	C23—C24—C25	119.46 (17)
C13—C12—H12	119.8	C24—O24—C27	118.77 (17)
C11—C12—H12	119.8	O24—C27—H27A	109.5
C14—C13—C12	120.8 (2)	O24—C27—H27B	109.5
C14—C13—H13	119.6	H27A—C27—H27B	109.5
C12—C13—H13	119.6	O24—C27—H27C	109.5
C13—C14—C15	120.0 (2)	H27A—C27—H27C	109.5
C13—C14—H14	120.0	H27B—C27—H27C	109.5
C15—C14—H14	120.0	C24—C25—C26	119.05 (17)
C14—C15—C16	120.2 (2)	C24—C25—H25	120.5
C14—C15—H15	119.9	C26—C25—H25	120.5
C16—C15—H15	119.9	C21—C26—C25	122.30 (18)
C11—C16—C15	119.8 (2)	C21—C26—H26	118.8
C11—C16—H16	120.1	C25—C26—H26	118.8
O2—C1—C2—O3	12.1 (3)	N4—C5—C6—C7	169.29 (17)
O1—C1—C2—O3	−168.96 (16)	C11—C5—C6—C7	−14.2 (3)
C1—C2—O3—N4	−80.63 (18)	C5—C6—C7—C21	179.27 (16)
C2—O3—N4—C5	174.60 (15)	C6—C7—C21—C26	−175.84 (18)
O3—N4—C5—C6	−1.6 (2)	C6—C7—C21—C22	2.8 (3)
O3—N4—C5—C11	−178.36 (14)	C26—C21—C22—C23	0.3 (3)
N4—C5—C11—C16	−53.7 (2)	C7—C21—C22—C23	−178.36 (17)
C6—C5—C11—C16	129.4 (2)	C21—C22—C23—C24	−0.1 (3)
N4—C5—C11—C12	121.89 (19)	C22—C23—C24—O24	179.32 (17)
C6—C5—C11—C12	−55.0 (2)	C22—C23—C24—C25	0.0 (3)
C16—C11—C12—C13	0.9 (3)	C23—C24—O24—C27	−178.57 (18)
C5—C11—C12—C13	−174.80 (19)	C25—C24—O24—C27	0.8 (3)
C11—C12—C13—C14	−0.6 (3)	O24—C24—C25—C26	−179.26 (18)
C12—C13—C14—C15	−0.9 (4)	C23—C24—C25—C26	0.0 (3)
C13—C14—C15—C16	2.2 (4)	C22—C21—C26—C25	−0.3 (3)
C12—C11—C16—C15	0.3 (3)	C7—C21—C26—C25	178.38 (17)
C5—C11—C16—C15	176.0 (2)	C24—C25—C26—C21	0.1 (3)
C14—C15—C16—C11	−1.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.82	1.86	2.679 (2)	175
C23—H23···N4^ii	0.93	2.56	3.472 (2)	167
C22—H22···Cg1^ii	0.93	2.94	3.712 (2)	141

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y+1/2, −z+1/2.

(III) (E)-[1-(4-methoxyphenyl)-3-phenyl-2-propenylideneamino)oxyacetic acid

Crystal data

C18H17NO4	F(000) = 1312
Mr = 311.33	Dx = 1.297 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7291 reflections
a = 12.1552 (4) Å	θ = 3.1–27.5°
b = 15.8657 (4) Å	µ = 0.09 mm^−1
c = 16.6708 (5) Å	T = 120 K
β = 97.4250 (15)°	Lath, colourless
V = 3188.02 (16) Å^3	0.50 × 0.40 × 0.10 mm
Z = 8

Data collection

Bruker-Nonius 95mm CCD camera on κ-goniostat diffractometer	7291 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	4714 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ϕ & ω scans	h = −15→15
Absorption correction: multi-scan SADABS V2.10 (Sheldrick, 2003)	k = −20→20
Tmin = 0.950, Tmax = 0.991	l = −21→21
37246 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0728P)^2 + 0.0298P] where P = (Fo^2 + 2Fc^2)/3
7291 reflections	(Δ/σ)max = 0.001
419 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O11	0.60212 (10)	0.56379 (9)	0.28717 (7)	0.0435 (4)
O12	0.42927 (11)	0.52190 (8)	0.29603 (7)	0.0411 (3)
O13	0.43379 (10)	0.58474 (7)	0.44360 (7)	0.0323 (3)
O124	−0.11867 (10)	0.29543 (7)	0.59410 (7)	0.0331 (3)
N14	0.42907 (12)	0.64910 (9)	0.50237 (8)	0.0290 (3)
C11	0.51295 (14)	0.55789 (11)	0.32369 (10)	0.0291 (4)
C12	0.52739 (15)	0.60170 (12)	0.40365 (11)	0.0352 (4)
C15	0.34766 (14)	0.63659 (10)	0.54340 (9)	0.0264 (4)
C16	0.26956 (14)	0.56694 (10)	0.53505 (9)	0.0280 (4)
C17	0.19449 (14)	0.55516 (10)	0.58655 (10)	0.0281 (4)
C111	0.33781 (14)	0.70341 (10)	0.60582 (9)	0.0269 (4)
C112	0.25273 (17)	0.76212 (12)	0.59476 (11)	0.0409 (5)
C113	0.24311 (18)	0.82324 (12)	0.65273 (11)	0.0444 (5)
C114	0.31780 (16)	0.82537 (11)	0.72226 (11)	0.0365 (4)
C115	0.40130 (15)	0.76687 (12)	0.73392 (11)	0.0391 (5)
C116	0.41229 (14)	0.70639 (12)	0.67570 (10)	0.0348 (4)
C121	0.11332 (14)	0.48772 (10)	0.58652 (9)	0.0269 (4)
C122	0.11024 (14)	0.41659 (10)	0.53648 (9)	0.0280 (4)
C123	0.03236 (14)	0.35489 (10)	0.54017 (10)	0.0290 (4)
C124	−0.04624 (14)	0.36190 (10)	0.59366 (9)	0.0268 (4)
C127	−0.19932 (15)	0.29812 (13)	0.64951 (11)	0.0388 (4)
C125	−0.04615 (14)	0.43180 (10)	0.64316 (10)	0.0290 (4)
C126	0.03363 (14)	0.49315 (10)	0.63944 (10)	0.0303 (4)
O21	0.40174 (10)	0.43730 (8)	0.15846 (7)	0.0350 (3)
O22	0.57373 (10)	0.48298 (8)	0.14661 (7)	0.0344 (3)
O23	0.56570 (9)	0.41308 (7)	−0.00042 (7)	0.0292 (3)
O224	1.13190 (9)	0.69604 (7)	−0.09055 (7)	0.0304 (3)
N24	0.58213 (11)	0.33839 (8)	−0.04476 (8)	0.0258 (3)
C21	0.48979 (14)	0.44498 (10)	0.12040 (10)	0.0276 (4)
C22	0.47239 (14)	0.39976 (10)	0.04122 (10)	0.0285 (4)
C25	0.67422 (13)	0.34212 (10)	−0.07630 (9)	0.0232 (3)
C26	0.75050 (13)	0.41265 (10)	−0.06827 (9)	0.0247 (4)
C27	0.83773 (13)	0.42128 (10)	−0.10911 (9)	0.0244 (4)
C211	0.69586 (13)	0.26371 (10)	−0.12096 (9)	0.0234 (4)
C212	0.78964 (14)	0.21562 (10)	−0.09741 (10)	0.0272 (4)
C213	0.80524 (14)	0.13922 (10)	−0.13449 (10)	0.0305 (4)
C214	0.72783 (15)	0.11144 (11)	−0.19686 (10)	0.0330 (4)
C215	0.63508 (15)	0.15915 (11)	−0.22151 (10)	0.0342 (4)
C216	0.61770 (14)	0.23510 (11)	−0.18340 (10)	0.0296 (4)
C221	0.91380 (13)	0.49278 (10)	−0.10393 (9)	0.0234 (4)
C222	0.89385 (13)	0.56883 (10)	−0.06499 (9)	0.0254 (4)
C223	0.96769 (14)	0.63421 (10)	−0.06110 (9)	0.0263 (4)
C224	1.06506 (13)	0.62654 (10)	−0.09646 (9)	0.0246 (4)
C227	1.22717 (15)	0.69469 (12)	−0.13253 (11)	0.0374 (4)
C225	1.08826 (13)	0.55199 (10)	−0.13456 (9)	0.0261 (4)
C226	1.01226 (13)	0.48678 (10)	−0.13817 (9)	0.0255 (4)
H11	0.5911	0.5390	0.2423	0.065*
H12A	0.5956	0.5814	0.4369	0.042*
H12B	0.5346	0.6632	0.3957	0.042*
H112	0.2007	0.7604	0.5471	0.049*
H113	0.1851	0.8636	0.6446	0.053*
H114	0.3115	0.8673	0.7621	0.044*
H115	0.4520	0.7679	0.7823	0.047*
H116	0.4713	0.6668	0.6838	0.042*
H16	0.2716	0.5283	0.4917	0.034*
H17	0.1944	0.5960	0.6282	0.034*
H122	0.1630	0.4111	0.4994	0.034*
H123	0.0319	0.3069	0.5060	0.035*
H12C	−0.2455	0.3485	0.6390	0.058*
H12D	−0.1614	0.2999	0.7051	0.058*
H12E	−0.2462	0.2477	0.6424	0.058*
H125	−0.1002	0.4376	0.6792	0.035*
H126	0.0342	0.5407	0.6741	0.036*
H21	0.4122	0.4637	0.2024	0.053*
H22A	0.4628	0.3387	0.0504	0.034*
H22B	0.4045	0.4211	0.0083	0.034*
H212	0.8438	0.2353	−0.0554	0.033*
H213	0.8689	0.1060	−0.1171	0.037*
H214	0.7386	0.0593	−0.2228	0.040*
H215	0.5825	0.1401	−0.2649	0.041*
H216	0.5528	0.2673	−0.1999	0.035*
H26	0.7377	0.4560	−0.0313	0.030*
H27	0.8513	0.3768	−0.1447	0.029*
H222	0.8276	0.5749	−0.0409	0.030*
H223	0.9526	0.6849	−0.0343	0.032*
H22C	1.2756	0.6479	−0.1124	0.056*
H22D	1.2676	0.7480	−0.1234	0.056*
H22E	1.2036	0.6873	−0.1906	0.056*
H225	1.1552	0.5459	−0.1577	0.031*
H226	1.0277	0.4361	−0.1649	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0307 (10)	0.0267 (9)	0.0316 (9)	−0.0005 (8)	0.0104 (8)	0.0013 (7)
O11	0.0345 (7)	0.0610 (9)	0.0377 (8)	−0.0131 (7)	0.0156 (6)	−0.0155 (6)
O12	0.0376 (7)	0.0514 (8)	0.0376 (7)	−0.0158 (7)	0.0177 (6)	−0.0152 (6)
C12	0.0310 (10)	0.0381 (10)	0.0385 (10)	−0.0020 (8)	0.0118 (8)	−0.0098 (8)
O13	0.0366 (7)	0.0296 (6)	0.0330 (7)	−0.0050 (6)	0.0132 (5)	−0.0097 (5)
N14	0.0338 (8)	0.0269 (8)	0.0262 (7)	0.0003 (6)	0.0040 (6)	−0.0066 (6)
C15	0.0296 (9)	0.0268 (9)	0.0220 (8)	0.0020 (8)	0.0008 (7)	0.0032 (7)
C111	0.0330 (9)	0.0244 (8)	0.0249 (9)	−0.0028 (8)	0.0093 (7)	0.0000 (7)
C112	0.0525 (12)	0.0370 (11)	0.0310 (10)	0.0113 (10)	−0.0030 (9)	−0.0033 (8)
C113	0.0592 (13)	0.0330 (10)	0.0417 (11)	0.0104 (10)	0.0094 (10)	−0.0056 (8)
C114	0.0461 (11)	0.0322 (10)	0.0349 (10)	−0.0142 (9)	0.0192 (9)	−0.0102 (8)
C115	0.0332 (10)	0.0507 (12)	0.0339 (10)	−0.0095 (10)	0.0061 (8)	−0.0147 (9)
C116	0.0260 (9)	0.0434 (11)	0.0354 (10)	0.0001 (8)	0.0054 (8)	−0.0058 (8)
C16	0.0349 (10)	0.0248 (9)	0.0245 (9)	0.0025 (8)	0.0048 (7)	−0.0023 (7)
C17	0.0344 (10)	0.0253 (9)	0.0246 (9)	0.0030 (8)	0.0036 (7)	−0.0014 (7)
C121	0.0313 (9)	0.0253 (9)	0.0242 (8)	0.0052 (8)	0.0041 (7)	0.0049 (7)
C122	0.0339 (10)	0.0267 (9)	0.0243 (9)	0.0054 (8)	0.0076 (7)	0.0024 (7)
C123	0.0371 (10)	0.0233 (9)	0.0275 (9)	0.0029 (8)	0.0076 (7)	−0.0017 (7)
C124	0.0304 (9)	0.0249 (8)	0.0247 (8)	0.0017 (8)	0.0022 (7)	0.0053 (7)
O124	0.0367 (7)	0.0309 (7)	0.0329 (7)	−0.0058 (6)	0.0094 (5)	0.0008 (5)
C127	0.0342 (10)	0.0457 (11)	0.0385 (10)	−0.0068 (9)	0.0123 (8)	0.0033 (9)
C125	0.0319 (9)	0.0313 (9)	0.0253 (9)	0.0035 (8)	0.0102 (7)	0.0008 (7)
C126	0.0403 (11)	0.0247 (9)	0.0268 (9)	0.0032 (8)	0.0079 (7)	−0.0012 (7)
C21	0.0281 (9)	0.0235 (9)	0.0329 (9)	0.0026 (8)	0.0113 (7)	0.0040 (7)
O21	0.0304 (7)	0.0436 (8)	0.0336 (7)	−0.0068 (6)	0.0142 (5)	−0.0096 (6)
O22	0.0309 (7)	0.0415 (7)	0.0326 (7)	−0.0067 (6)	0.0109 (5)	−0.0060 (5)
C22	0.0281 (9)	0.0236 (8)	0.0363 (9)	−0.0022 (8)	0.0143 (7)	−0.0029 (7)
O23	0.0318 (7)	0.0220 (6)	0.0372 (7)	−0.0035 (5)	0.0169 (5)	−0.0064 (5)
N24	0.0321 (8)	0.0185 (7)	0.0279 (7)	−0.0002 (6)	0.0076 (6)	−0.0051 (5)
C25	0.0240 (9)	0.0250 (8)	0.0205 (8)	0.0000 (7)	0.0028 (6)	0.0011 (6)
C211	0.0236 (8)	0.0251 (8)	0.0228 (8)	−0.0051 (7)	0.0080 (7)	−0.0003 (6)
C212	0.0264 (9)	0.0273 (9)	0.0282 (9)	−0.0044 (7)	0.0055 (7)	−0.0020 (7)
C213	0.0282 (9)	0.0264 (9)	0.0390 (10)	−0.0012 (8)	0.0121 (8)	−0.0025 (7)
C214	0.0351 (10)	0.0286 (9)	0.0384 (10)	−0.0067 (8)	0.0166 (8)	−0.0106 (8)
C215	0.0342 (10)	0.0393 (10)	0.0298 (9)	−0.0118 (9)	0.0068 (8)	−0.0119 (8)
C216	0.0267 (9)	0.0344 (10)	0.0275 (9)	−0.0027 (8)	0.0032 (7)	−0.0025 (7)
C26	0.0268 (9)	0.0232 (8)	0.0239 (8)	0.0009 (7)	0.0029 (7)	−0.0020 (6)
C27	0.0277 (9)	0.0220 (8)	0.0237 (8)	0.0010 (7)	0.0040 (7)	−0.0027 (6)
C221	0.0238 (9)	0.0240 (8)	0.0222 (8)	−0.0004 (7)	0.0025 (6)	0.0006 (6)
C222	0.0231 (9)	0.0275 (9)	0.0264 (9)	0.0015 (7)	0.0066 (7)	0.0002 (7)
C223	0.0293 (9)	0.0239 (8)	0.0260 (9)	0.0005 (7)	0.0044 (7)	−0.0017 (7)
C224	0.0245 (9)	0.0270 (9)	0.0213 (8)	−0.0038 (7)	−0.0012 (6)	0.0028 (6)
O224	0.0290 (6)	0.0282 (6)	0.0348 (7)	−0.0081 (5)	0.0073 (5)	−0.0010 (5)
C227	0.0321 (10)	0.0422 (11)	0.0393 (10)	−0.0120 (9)	0.0095 (8)	0.0003 (8)
C225	0.0235 (9)	0.0296 (9)	0.0262 (9)	0.0023 (7)	0.0066 (7)	0.0014 (7)
C226	0.0265 (9)	0.0248 (8)	0.0259 (9)	0.0033 (7)	0.0066 (7)	−0.0020 (7)

Geometric parameters (Å, º)

C11—O12	1.205 (2)	C21—O22	1.217 (2)
C11—O11	1.3133 (19)	C21—O21	1.3184 (19)
C11—C12	1.493 (2)	C21—C22	1.493 (2)
O11—H11	0.84	O21—H21	0.84
C12—O13	1.416 (2)	C22—O23	1.4200 (18)
C12—H12A	0.99	C22—H22A	0.99
C12—H12B	0.99	C22—H22B	0.99
O13—N14	1.4214 (16)	O23—N24	1.4243 (16)
N14—C15	1.289 (2)	N24—C25	1.298 (2)
C15—C16	1.452 (2)	C25—C26	1.448 (2)
C15—C111	1.501 (2)	C25—C211	1.491 (2)
C111—C116	1.381 (2)	C211—C212	1.386 (2)
C111—C112	1.386 (2)	C211—C216	1.392 (2)
C112—C113	1.385 (2)	C212—C213	1.385 (2)
C112—H112	0.95	C212—H212	0.95
C113—C114	1.377 (3)	C213—C214	1.381 (2)
C113—H113	0.95	C213—H213	0.95
C114—C115	1.370 (3)	C214—C215	1.376 (3)
C114—H114	0.95	C214—H214	0.95
C115—C116	1.383 (2)	C215—C216	1.391 (2)
C115—H115	0.95	C215—H215	0.95
C116—H116	0.95	C216—H216	0.95
C16—C17	1.344 (2)	C26—C27	1.339 (2)
C16—H16	0.95	C26—H26	0.95
C17—C121	1.455 (2)	C27—C221	1.459 (2)
C17—H17	0.95	C27—H27	0.95
C121—C126	1.395 (2)	C221—C226	1.394 (2)
C121—C122	1.401 (2)	C221—C222	1.406 (2)
C122—C123	1.369 (2)	C222—C223	1.368 (2)
C122—H122	0.95	C222—H222	0.95
C123—C124	1.393 (2)	C223—C224	1.394 (2)
C123—H123	0.95	C223—H223	0.95
C124—O124	1.374 (2)	C224—O224	1.3655 (19)
C124—C125	1.382 (2)	C224—C225	1.389 (2)
O124—C127	1.432 (2)	O224—C227	1.428 (2)
C127—H12C	0.98	C227—H22C	0.98
C127—H12D	0.98	C227—H22D	0.98
C127—H12E	0.98	C227—H22E	0.98
C125—C126	1.381 (2)	C225—C226	1.383 (2)
C125—H125	0.95	C225—H225	0.95
C126—H126	0.95	C226—H226	0.95
O12—C11—O11	124.25 (15)	O22—C21—O21	124.63 (15)
O12—C11—C12	123.92 (15)	O22—C21—C22	124.88 (15)
O11—C11—C12	111.82 (15)	O21—C21—C22	110.49 (14)
C11—O11—H11	109.5	C21—O21—H21	109.5
O13—C12—C11	108.81 (14)	O23—C22—C21	109.27 (13)
O13—C12—H12A	109.9	O23—C22—H22A	109.8
C11—C12—H12A	109.9	C21—C22—H22A	109.8
O13—C12—H12B	109.9	O23—C22—H22B	109.8
C11—C12—H12B	109.9	C21—C22—H22B	109.8
H12A—C12—H12B	108.3	H22A—C22—H22B	108.3
C12—O13—N14	107.10 (12)	C22—O23—N24	107.72 (11)
C15—N14—O13	110.93 (13)	C25—N24—O23	111.00 (12)
N14—C15—C16	127.14 (15)	N24—C25—C26	124.97 (14)
N14—C15—C111	113.24 (14)	N24—C25—C211	112.42 (13)
C16—C15—C111	119.62 (14)	C26—C25—C211	122.60 (14)
C116—C111—C112	119.06 (16)	C212—C211—C216	119.30 (15)
C116—C111—C15	120.45 (15)	C212—C211—C25	120.66 (14)
C112—C111—C15	120.49 (15)	C216—C211—C25	119.89 (15)
C113—C112—C111	120.44 (18)	C213—C212—C211	120.70 (16)
C113—C112—H112	119.8	C213—C212—H212	119.6
C111—C112—H112	119.8	C211—C212—H212	119.6
C114—C113—C112	119.91 (19)	C214—C213—C212	119.75 (16)
C114—C113—H113	120.0	C214—C213—H213	120.1
C112—C113—H113	120.0	C212—C213—H213	120.1
C115—C114—C113	119.89 (17)	C215—C214—C213	120.09 (15)
C115—C114—H114	120.1	C215—C214—H214	120.0
C113—C114—H114	120.1	C213—C214—H214	120.0
C114—C115—C116	120.47 (17)	C214—C215—C216	120.47 (16)
C114—C115—H115	119.8	C214—C215—H215	119.8
C116—C115—H115	119.8	C216—C215—H215	119.8
C111—C116—C115	120.23 (17)	C215—C216—C211	119.67 (16)
C111—C116—H116	119.9	C215—C216—H216	120.2
C115—C116—H116	119.9	C211—C216—H216	120.2
C17—C16—C15	122.28 (15)	C27—C26—C25	124.86 (14)
C17—C16—H16	118.9	C27—C26—H26	117.6
C15—C16—H16	118.9	C25—C26—H26	117.6
C16—C17—C121	128.17 (15)	C26—C27—C221	125.93 (15)
C16—C17—H17	115.9	C26—C27—H27	117.0
C121—C17—H17	115.9	C221—C27—H27	117.0
C126—C121—C122	117.33 (15)	C226—C221—C222	117.13 (14)
C126—C121—C17	118.72 (15)	C226—C221—C27	119.58 (14)
C122—C121—C17	123.95 (15)	C222—C221—C27	123.28 (14)
C123—C122—C121	120.99 (15)	C223—C222—C221	121.43 (15)
C123—C122—H122	119.5	C223—C222—H222	119.3
C121—C122—H122	119.5	C221—C222—H222	119.3
C122—C123—C124	120.48 (15)	C222—C223—C224	120.11 (15)
C122—C123—H123	119.8	C222—C223—H223	119.9
C124—C123—H123	119.8	C224—C223—H223	119.9
O124—C124—C125	124.30 (15)	O224—C224—C225	124.52 (14)
O124—C124—C123	115.78 (14)	O224—C224—C223	115.39 (14)
C125—C124—C123	119.90 (15)	C225—C224—C223	120.09 (15)
C124—O124—C127	118.23 (13)	C224—O224—C227	117.71 (13)
O124—C127—H12C	109.5	O224—C227—H22C	109.5
O124—C127—H12D	109.5	O224—C227—H22D	109.5
H12C—C127—H12D	109.5	H22C—C227—H22D	109.5
O124—C127—H12E	109.5	O224—C227—H22E	109.5
H12C—C127—H12E	109.5	H22C—C227—H22E	109.5
H12D—C127—H12E	109.5	H22D—C227—H22E	109.5
C126—C125—C124	119.02 (15)	C226—C225—C224	118.89 (15)
C126—C125—H125	120.5	C226—C225—H225	120.6
C124—C125—H125	120.5	C224—C225—H225	120.6
C125—C126—C121	122.27 (15)	C225—C226—C221	122.34 (15)
C125—C126—H126	118.9	C225—C226—H226	118.8
C121—C126—H126	118.9	C221—C226—H226	118.8
O12—C11—C12—O13	7.0 (2)	O22—C21—C22—O23	−3.9 (2)
O11—C11—C12—O13	−173.35 (14)	O21—C21—C22—O23	176.70 (13)
C11—C12—O13—N14	−158.92 (13)	C21—C22—O23—N24	145.91 (13)
C12—O13—N14—C15	−177.91 (14)	C22—O23—N24—C25	−172.06 (13)
O13—N14—C15—C16	1.1 (2)	O23—N24—C25—C26	−0.3 (2)
O13—N14—C15—C111	−179.28 (12)	O23—N24—C25—C211	178.15 (12)
N14—C15—C111—C116	−73.7 (2)	N24—C25—C211—C212	−119.08 (16)
C16—C15—C111—C116	105.94 (19)	C26—C25—C211—C212	59.4 (2)
N14—C15—C111—C112	107.38 (19)	N24—C25—C211—C216	56.44 (19)
C16—C15—C111—C112	−73.0 (2)	C26—C25—C211—C216	−125.06 (17)
C116—C111—C112—C113	0.5 (3)	C216—C211—C212—C213	−1.0 (2)
C15—C111—C112—C113	179.39 (17)	C25—C211—C212—C213	174.59 (14)
C111—C112—C113—C114	−0.6 (3)	C211—C212—C213—C214	1.5 (2)
C112—C113—C114—C115	−0.1 (3)	C212—C213—C214—C215	−0.6 (3)
C113—C114—C115—C116	1.1 (3)	C213—C214—C215—C216	−0.8 (3)
C112—C111—C116—C115	0.5 (3)	C214—C215—C216—C211	1.3 (2)
C15—C111—C116—C115	−178.47 (16)	C212—C211—C216—C215	−0.4 (2)
C114—C115—C116—C111	−1.2 (3)	C25—C211—C216—C215	−175.98 (14)
N14—C15—C16—C17	172.97 (16)	N24—C25—C26—C27	−170.89 (15)
C111—C15—C16—C17	−6.6 (2)	C211—C25—C26—C27	10.8 (2)
C15—C16—C17—C121	−178.62 (15)	C25—C26—C27—C221	178.06 (15)
C16—C17—C121—C126	−171.99 (17)	C26—C27—C221—C226	168.28 (15)
C16—C17—C121—C122	8.3 (3)	C26—C27—C221—C222	−11.1 (3)
C126—C121—C122—C123	−0.5 (2)	C226—C221—C222—C223	0.2 (2)
C17—C121—C122—C123	179.22 (15)	C27—C221—C222—C223	179.62 (15)
C121—C122—C123—C124	0.4 (3)	C221—C222—C223—C224	0.3 (2)
C122—C123—C124—O124	−178.29 (14)	C222—C223—C224—O224	178.72 (14)
C122—C123—C124—C125	0.3 (2)	C222—C223—C224—C225	−1.1 (2)
C125—C124—O124—C127	−0.3 (2)	C225—C224—O224—C227	5.8 (2)
C123—C124—O124—C127	178.30 (14)	C223—C224—O224—C227	−173.96 (13)
O124—C124—C125—C126	177.48 (15)	O224—C224—C225—C226	−178.40 (14)
C123—C124—C125—C126	−1.0 (2)	C223—C224—C225—C226	1.4 (2)
C124—C125—C126—C121	1.0 (3)	C224—C225—C226—C221	−0.9 (2)
C122—C121—C126—C125	−0.3 (2)	C222—C221—C226—C225	0.1 (2)
C17—C121—C126—C125	−179.95 (15)	C27—C221—C226—C225	−179.32 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O11—H11···O22	0.84	1.81	2.6542 (17)	177
O21—H21···O12	0.84	1.80	2.6410 (17)	178
C215—H215···Cg2^i	0.95	2.64	3.532 (2)	157

Symmetry code: (i) −x+3/2, y−1/2, −z−1/2.

 

Footnotes

‡Postal address: School of Engineering & Physics, University of Dundee, Dundee DD1 4HN, Scotland.

¹Supplementary data for this paper are available from the IUCr electronic archives (Reference: WS5022 ). Services for accessing these data are described at the back of the journal.