Do carboximide–carboxylic acid combinations form co-crystals? The role of hydroxyl substitution on the formation of co-crystals and eutectics

Carboxylic acids, amides and imides are key organic systems which provide understanding of molecular recognition and binding phenomena important in biological and pharmaceutical settings. In this context, studies of their mutual interactions and compatibility through co-crystallization may pave the way for greater understanding and new applications of their combinations. Extensive co-crystallization studies are available for carboxylic acid/amide combinations, but only a few examples of carboxylic acid/imide co-crystals are currently observed in the literature. The non-formation of co-crystals for carboxylic acid/imide combinations has previously been rationalized, based on steric and computed stability factors. In the light of the growing awareness of eutectic mixtures as an alternative outcome in co-crystallization experiments, the nature of various benzoic acid/cyclic imide combinations is established in this paper. Since an additional functional group can provide sites for new intermolecular inter­actions and, potentially, promote supramolecular growth into a co-crystal, benzoic acids decorated with one or more hydroxyl groups have been systematically screened for co-crystallization with one unsaturated and two saturated cyclic imides. The facile formation of an abundant number of hydroxybenzoic acid/cyclic carboximide co-crystals is reported, including polymorphic and variable stoichiometry co-crystals. In the cases where co-crystals did not form, the combinations are shown invariably to result in eutectics. The presence or absence and geometric disposition of hydroxyl functionality on benzoic acid is thus found to drive the formation of co-crystals or eutectics for the studied carboxylic acid/imide combinations.

1. Introduction

There is a renewed interest in understanding the chemical factors that govern the phenomenon of co-crystallization (Cherukuvada & Row, 2014; Prasad et al., 2014; Wood et al., 2014; Mukherjee et al., 2014; Aitipamula, Chow & Tan, 2014; Bučar et al., 2013; Seaton & Parkin, 2011; Braga et al., 2010; Friščić & Jones, 2009; Lu et al., 2008; Aakeröy et al., 2008; Chadwick et al., 2007; Friščić et al., 2006; Shan et al., 2002), owing largely to its potential importance in the pharma­ceutical industry (Cherukuvada & Nangia, 2014; Aakeröy et al., 2014; Brittain, 2012; Babu & Nangia, 2011; Chen et al., 2011; Schultheiss & Newman, 2009; Shan & Zaworotko, 2008; Blagden et al., 2007; Trask & Jones, 2005). Co-crystallization is a supramolecular reaction to form multi-component organic adducts such as co-crystals, solid solutions, eutectics etc. (Cherukuvada & Nangia, 2014; Cherukuvada & Row, 2014; Prasad et al., 2014). Whether a co-crystal or a eutectic is formed depends on the dominance of hetero- and homomolecular interactions, respectively, for a given combination of materials. Several aspects play a role in the formation of co-crystals and eutectics, such as the nature and influence of the molecular components in invoking intermolecular interactions and supramolecular synthons, functional group disposition and complementarity, interaction strength, and efficient packing. However, there is no general recipe to obtain selectively or reliably either co-crystals or eutectics on demand. Investigations into this effect are important to save time, money and effort in targeted co-crystal or eutectic screens.

The literature describes numerous failed co-crystallization experiments (for example, Alhalaweh et al., 2012; Arenas-García et al., 2012; Seaton & Parkin, 2011; Caira et al., 2012; Mohammad et al., 2011; Karki et al., 2010), which did not investigate the potential formation of eutectics. Given their potential importance in the pharmaceutical and materials fields (Cherukuvada & Nangia, 2014; Griffini et al., 2014; Huang et al., 2013; Yan et al., 2011; Morimoto & Irie, 2010; Karaipekli & Sarı, 2010; Schultheiss & Newman, 2009; Moore & Wildfong, 2009), there is a need for more studies of the attributes that govern co-crystal/eutectic formation. Exploring systems with subtle differences in hydrogen-bonding functional groups can serve as a lead, since these groups can steer supramolecular growth as either a co-crystal or a eutectic for a given combination (Cherukuvada & Nangia, 2014; Cherukuvada & Row, 2014; Prasad et al., 2014). In this context, we have selected cyclic carboximides for an in-depth co-crystallization study with carboxylic acids. The latter class of compounds has a wide variety of applications, particularly in the pharmaceutical field, as drugs, salts and co-formers, excipients etc. (Cherukuvada & Nangia, 2014; Aitipamula, Wong et al., 2014; Ballatore et al., 2013; Losev et al., 2013; Ebenezer & Muthiah, 2012, Reddy et al., 2011; Seaton, 2011; Moffat et al., 2011; Rowe et al., 2006; Caira et al., 1995; Gould, 1986). Likewise, amide (primary and secondary) and imide functionalities are found in several drugs and are amenable to both salt and co-crystal formation (Buist et al., 2013; Sanphui et al., 2013; Nanubolu et al., 2012; Cherukuvada & Nangia, 2012; Moffat et al., 2011; Cherukuvada et al., 2011). Therefore, the study of the interactions and compatibility of amide/imide–carboxylic acid combinations has direct practical significance.

Co-crystallization of carboxylic acids with amides has been studied extensively (Cherukuvada & Row, 2014; Moragues-Bartolome et al., 2012; Kaur & Row, 2012; Babu et al., 2012; Cherukuvada & Nangia, 2012; Reddy et al., 2007; McMahon et al., 2005; Leiserowitz & Nader, 1977), whereas only limited studies of carboxylic acid/imide combinations are found in the literature. The prospect for co-crystal formation involving carboximide and carboxylic acid groups has been considered (Moragues-Bartolome et al., 2012), and it was suggested that these groups are not expected to interact within co-crystals. Moragues-Bartolome et al. (2012) reported the co-crystallization of saturated cyclic imides (succinimide and glutarimide) with a variety of aliphatic and aromatic monocarboxylic acids and obtained only one co-crystal, namely succinimide–2,4-di­hydroxy­benzoic acid (SM–24DHBA), as shown in Fig. 1. Based on the steric hindrance of the extra imide carbonyl group and the low stabilizing features of imide–acid and acid-supported imide–imide hydrogen-bonding motifs (named T_hetero and T_homo units, respectively; Fig. 2) compared with amides, they deduced that the formation of cyclic imide–carboxylic acid co-crystals is unlikely. The study considered carboxylic acid–imide combinations, of which the majority had hydrogen-bond acceptor groups (fluoro, nitro etc.) on the acid partner. Since the hydrogen-bond demands of the extra imide carbonyl acceptor cannot be complemented by acceptor groups on the partner molecules, co-crystal formation is curtailed due to high-energy interactions (repulsions) associated with acceptor–acceptor (carbonyl versus fluoro/nitro) combinations. It is understandable that a hydrogen-bond donor like hydroxyl can satisfy the imide carbonyl and therefore lead to the SM–24DHBA co-crystal (Figs. 1 and 2c).

Figure 1 The succinimide–2,4-dihydroxybenzoic acid (SM–24DHBA) co-crystal (Moragues-Bartolome et al., 2012). The structure shows acid-flanked imide homodimers (Thomo units, Fig. 2) propagated by hydroxyl–carbonyl hydrogen bonds (dotted lines) involving the para-hydroxyl group of 24DHBA. We designate this as polymorph I, with polymorph II reported herein.

Figure 2 (a) The tetrameric unit of two carboxylic acid–imide heterodimers. (b) The tetrameric unit of an acid-flanked imide homodimer. Both (a) and (b) have been calculated to be less stable (Moragues-Bartolome et al., 2012) and hence less likely to occur in co-crystals. (c) The reported SM–24DHBA co-crystal shows the Thomo unit, with the crucial stabilization and propagation of the unit via para-OH⋯carbonyl (imide) hydrogen bonds. Dashed lines indicate hydrogen bonds.

In the context of eutectics as alternative supramolecular assemblies to co-crystals (Cherukuvada & Nangia, 2014; Cherukuvada & Row, 2014; Prasad et al., 2014), and with the hypothesis that auxiliary interactions play a crucial role, we undertook the task of establishing the nature of different imide–carboxylic acid combinations. We selected for study three cyclic imides (succinimide, glutarimide and maleimide, which is unsaturated) and seven hydroxybenzoic acids, in addition to the parent benzoic acid (Fig. 3). The rationale for the selection of hydroxybenzoic acids is that the presence of hydroxyl group(s) on the benzoic acid molecule would instigate auxiliary interactions with the extra imide carbonyl, thereby facilitating supramolecular growth units beyond T_hetero or T_homo units (Fig. 2). We devised a scheme of dimeric and tetrameric hydrogen-bonded units that could form in carboxylic acid/imide combinations (Fig. 4). We perceive that the supramolecular propagation of these units should lead to the formation of co-crystals, with eutectics being formed otherwise (Fig. 4). We were successful in obtaining several co-crystals and eutectics of cyclic imide–hydroxybenzoic acids. We also obtained a new polymorph for the reported succin­imide–2,4-dihydroxybenzoic acid co-crystal (SM–24DHBA) and a new dimorphic pair of 2:1 succinimide–3,4,5-tri­hydroxy­benzoic acid co-crystals. This work demonstrates that the presence or absence of hydroxyl group(s) dictates the formation or non-formation of imide–carboxylic acid co-crystals in the systems studied here.

Figure 3 Molecular structures and acronyms. Moragues-Bartolome et al. (2012) previously obtained a co-crystal for the SM–24DHBA combination and reported that the SM–BA and GM–BA combinations lead to physical mixtures.

Figure 4 (a) The homodimeric and (b) the heterodimeric primary recognition units of cyclic imide–hydroxybenzoic acid combinations. (c) A tetrameric unit comprising a hydroxyl-supported imide homodimer (Thomo-II) can propagate through carboxylic acid homodimers to form co-crystals. (d) and (e) Similarly, the progression of tetrameric units can result in co-crystals. (f) Propagation of the Thetero unit can take place through OH substitution at meta-positions (indicated by red circles), which confers stronger O—Hhydroxyl⋯O=Cimide auxiliary interactions (compared with C—H⋯O=C) and therefore gives rise to co-crystals. Dashed lines indicate hydrogen bonds. Eutectics, which are hallmarked by finite and discrete units, can be formed for combinations where tetrameric units are not stabilized and/or propagated.

2. Results and discussion

We performed co-crystallization by solution crystallization, following both neat (Trask & Jones, 2005) and liquid-assisted grinding (Friščić et al., 2006; Shan et al., 2002) of all combinations (see §S1 in the supporting information for experimental details). Ground products were subjected to powder X-ray diffraction (PXRD) and melting-point determination to ascertain co-crystal/eutectic formation, on the basis that the former exhibit distinct PXRD patterns and melting behaviour while the latter display only a depression of the melting point compared with the parent materials (Cherukuvada & Nangia, 2014; Cherukuvada & Row, 2014; Prasad et al., 2014). X-ray single-crystal structures were determined for co-crystals (except for a few where suitable single crystals were not obtained) and phase diagrams were constructed for eutectics. The results of the co-crystallization experiments are listed in Table 1. Benzoic acid and the mono-hydroxybenzoic acids, except the 4-hydroxy isomer, gave eutectics with all three cyclic imides (Table 1). Along with 4-hydroxybenzoic acid (4HBA), all the di- and tri-hydroxybenzoic acids resulted in co-crystals with all three imides. A new polymorph of the reported succinimide–24DHBA co-crystal and a dimorphic pair of 2:1 succinimide–345THBA co-crystals were also obtained (Table 1). Crystallographic parameters of the co-crystals are given in §S2 of the supporting information . Comparison of the experimental PXRD patterns with the respective parent materials is provided in §§S3 and S4 of the supporting information in order to differentiate the co-crystal- and eutectic-forming combinations.

Table 1
Crystallization results for the imide–carboxylic acid combinations

	Succinimide (SM)	Maleimide (MM)	Glutarimide (GM)
Benzoic acid (BA)	Eutectic	Eutectic	Eutectic
2-Hydroxybenzoic acid (2HBA)	Eutectic	Eutectic	Eutectic
3-Hydroxybenzoic acid (3HBA)	Eutectic	Eutectic	Eutectic
4-Hydroxybenzoic acid (4HBA)	1:1 Co-crystal	1:1 Co-crystal	1:2 Co-crystal
2,4-Dihydroxybenzoic acid (24DHBA)	1:1 Co-crystal (two polymorphs)	1:1 Co-crystal	Co-crystal (by PXRD)
3,4-Dihydroxybenzoic acid (34DHBA)	1:2 Co-crystal	Co-crystal (by PXRD)	Co-crystal (by PXRD)
3,5-Dihydroxybenzoic acid (35DHBA)	1:3:3 Co-crystal hydrate	1:3:3 Co-crystal hydrate	1:1 Co-crystal
3,4,5-Trihydroxybenzoic acid (345THBA)	2:1 Co-crystal (two polymorphs)	Co-crystal (by PXRD)	Co-crystal (by PXRD)

2.1. Rationale for the formation of co-crystals or eutectics

The primary supramolecular recognition units in an imide–carboxylic acid combination are imide–imide, acid–acid and acid (COOH)–imide (CONH or COCH) centrosymmetric ring dimer motifs (Figs. 4a and 4b). If these units, either homo- or heterodimers, can extend through auxiliary interactions (such as O—H/C—H_{carboxylic acid}⋯O=C_imide) to form T_homo or T_hetero tetramers and then propagate, the formation of a co-crystal is facile, as per Fig. 4. On the other hand, a eutectic mixture results if the units remain finite and discrete in the supramolecular lattice (Cherukuvada & Nangia, 2014; Cherukuvada & Row, 2014; Prasad et al., 2014). We observed several intriguing results from the co-crystallization experiments: (i) all cyclic imides formed co-crystals with para-hydroxy substituted and di- or tri-hydroxy benzoic acids; (ii) non-formation of co-crystals in the case of benzoic acid and ortho- or meta-hydroxybenzoic acids, which instead formed eutectics; (iii) polymorphism in co-crystals; (iv) variable stoichiometry co-crystals; and (v) diverse co-crystal architectures. These features can be rationalized as follows.

First, the geometric positioning of a para-hydroxyl group aptly fits and promotes the supramolecular geometry of the T_homo unit (Figs. 2 and 4) to give co-crystals. By contrast, ortho- or meta-hydroxyl substitution provides no energetic stabilization to either T_hetero or T_homo supramolecular growth units and hence results in eutectic phases with all three cyclic imides. In the ortho-position, the hydroxyl group always participates in intramolecular hydrogen bonding with the carboxylic acid (O—H_hydroxyl⋯O=C_acid), such that it is unavailable for auxiliary interactions with the imide carbonyl group, and therefore propagation of T_hetero or T_homo units does not take place. Although it would seem that the meta-hydroxyl substituent could promote the T_homo unit, geometric reasons appear to resist supramolecular growth into a co-crystal. On the other hand, a meta-hydroxyl group fits the geometry and can stabilize the T_hetero unit. However, the stabilizing interactions from a lone meta-hydroxyl group seem to be insufficient and an additional substitution at the other meta-position is required for the T_hetero unit to propagate into a co-crystal (Fig. 4f). Thus, 35DHBA can distinctly form a T_hetero unit in its co-crystals and indeed it is found in the 1:1 GM–35DHBA co-crystal (as described later). It should be noted that a para-hydroxyl group does not suit the T_hetero unit and so cannot result in co-crystals for the same geometric reasons. In view of the above, it is obvious that unsubstituted benzoic acid forms only eutectics with the three cyclic imides. The hydrogen-bond demands of the additional strong imide carbonyl may not be satisfied by weak C—H donors (of benzoic acid) nor even by a strong hydroxyl group donor in a certain geometry (ortho- or meta-position of substituted benzoic acid), such that these combinations cannot make co-crystal growth units and therefore form eutectics.

Secondly, the crystal structure of the reported SM–24DHBA co-crystal (Moragues-Bartolome et al., 2012) (Fig. 1) supports our explanation of co-crystal/eutectic formation for different imide–carboxylic acid combinations in this study. Based on the above, it is reasonable to expect that all three imides can form co-crystals with the para-hydroxy substituted benzoic acids considered (Table 1). On the other hand, several co-crystals were obtained with supramolecular patterns different from those illustrated in Figs. 2 and 4, and they crystallized in different polymorphs and multiple stoichiometries. The crystal structures of the obtained cyclic imide–hydroxybenzoic acid co-crystals are discussed next, followed by phase diagrams for the eutectic-forming combinations.

2.2. Succinimide–hydroxybenzoic acid co-crystals

2.2.1. 1:1 SM–4HBA

In this crystal structure, T_homo-IV units (composed of succinimide C—H⋯O homodimers and imide–hydroxyphenyl heterodimers) propagate into tapes through carboxylic acid dimers (Fig. 5). Such tapes extend into two-dimensional sheets through O—H_hydroxy⋯O=C_imide and multiple C—H⋯O hydrogen bonds. The hydroxyl group clearly plays a major role in invoking auxiliary interactions and sustaining both the one- and two-dimensional motifs.

Figure 5 The structure of the 1:1 SM–4HBA co-crystal. Thomo-IV units are connected by 4HBA carboxylic acid homodimers to make parallel tapes that extend into a sheet through O—Hhydroxy⋯O=Cimide and multiple C—H⋯O interactions. The strong imide carbonyl acceptors are involved in multifurcated hydrogen bonds. Dotted lines indicate hydrogen bonds.

2.2.2. 1:1 SM–24DHBA, polymorph II

Crystallization of a 1:1 SM–24DHBA ground mixture in an effort to reproduce the reported 1:1 co-crystal (polymorph I; Moragues-Bartolome et al., 2012) resulted in a new polymorph of the co-crystal (polymorph II). This dimorphic pair represents a case of conformational and synthon polymorphism (Aitipamula, Chow & Tan, 2014; Aitipamula, Wong et al., 2014). The polymorphs differ in the conformation of the para-hydroxyl group, which is trans to the carbonyl of the acid group in polymorph I, and cis in polymorph II (Figs. 1 and 6). Whereas polymorph I shows the acid-flanked imide homodimer (T_homo-I unit, Fig. 1), polymorph II displays no imide or acid homodimer (Fig. 6). Instead, imide–hydroxyphenyl SM–24DHBA heterodimers permit the extra imide carbonyl and free acid groups to form hydrogen bonds with each other, propagating into a zigzag tape. Such tapes extend into a sheet structure through hydroxy–carbonyl_imide and C—H⋯O interactions. The absence of strong imide N—H⋯O or acid homodimers or imide–acid heterodimers in the co-crystal seems to be compensated by maximal intermolecular hydrogen bonding.

Figure 6 The structure of polymorph II of the 1:1 SM–24DHBA co-crystal. Parallel zigzag tapes formed by imide–hydroxyphenyl heterodimers between SM and 24DHBA molecules extend into a sheet through acid–carbonyl, hydroxyl–carbonyl and C—H⋯O interactions. The para-hydroxyl conformation in 24DHBA is cis with respect to the carbonyl of the acid group. Dotted lines indicate hydrogen bonds.

2.2.3. 1:2 SM–34DHBA

Crystallization of a 1:1 SM–34DHBA ground mixture from acetonitrile resulted in a co-crystal with 1:2 stoichiometry. In the crystal structure of 1:2 SM–34DHBA, N—H⋯O dimers between inversion-related SM molecules make T_homo-II units with their peripheral carbonyls hydrogen-bonded to hydroxyl groups of 34DHBA molecules (Fig. 7). These units propagate through acid homodimers between symmetry-independent 34DHBA molecules which have differences in their hydroxyl conformations (cis–cis in one case and trans–trans in the other with respect to the carbonyl of the acid group).

Figure 7 The structure of the 1:2 SM–34DHBA co-crystal. Thomo-II units propagate into tapes through acid homodimers formed by symmetry-independent 34DHBA molecules (shown in different colours), which have different hydroxyl conformations. Dotted lines indicate hydrogen bonds.

2.2.4. 1:3:3 SM–35DHBA–H₂O

Co-crystallization of SM and 35DHBA was expected to provide a 1:1 co-crystal having exclusively T_hetero units, as per the geometric features outlined in Fig. 4. Interestingly, however, a hydrated co-crystal with stoichiometry 1:3:3 SM–35DHBA–H₂O was obtained upon crystallization from methanol. In the crystal structure, planar hexameric motifs of 35DHBA molecules make voids that are filled by succinimide N—H⋯O dimers and water molecules (Fig. 8). The co-crystal is stabilized by forming a network of O—H⋯O interactions involving the hydroxyl groups and water molecules. On the basis of constructing an extended in-plane hydrogen-bond network, the hydroxyl groups of one of the three symmetry-independent 35DHBA molecules appear to be disordered.

Figure 8 The structure of the 1:3:3 SM–35DHBA–H2O co-crystal hydrate. Parallel hexameric motifs formed by symmetry-independent 35DHBA molecules (shown in different colours) make voids for the succinimide and water molecules. Dotted lines indicate hydrogen bonds. The disorder of the H atoms is not shown.

2.2.5. 2:1 SM–345THBA polymorphs

Crystallization of a 1:1 SM–345THBA ground mixture from methanol resulted in two polymorphs of a 2:1 co-crystal, designated polymorph I (space group P2₁2₁2₁) and polymorph II (space group ). In polymorph I, the hydroxyl groups of 345THBA have a cis–cis–trans geometry, while they have an all-trans geometry in polymorph II (Fig. 9). In polymorph I, N—H⋯O dimers between SM molecules permit the peripheral imide carbonyls to accept hydrogen bonds from acid and hydroxyl OH groups and propagate a tape (Fig. 9a). In polymorph II, N—H⋯O dimers between inversion-related SM molecules make T_homo-II units with the peripheral carbonyls, supported by hydrogen bonds from the hydroxyl groups of 345THBA molecules (Fig. 9b). Additionally, the outlying imide carbonyl of each SM molecule accepts a hydrogen bond from the imide NH of another SM molecule in an orthogonal manner. This dimorphic pair of co-crystals also exhibits conformational and synthon polymorphism (Aitipamula, Chow & Tan, 2014; Aitipamula, Wong et al., 2014).

Figure 9 (a) Polymorph I of the 2:1 SM–345THBA co-crystal. An infinite tape is formed by N—H⋯O dimers between symmetry-independent SM molecules (shown in different colours), with peripheral imide carbonyls involved in hydrogen bonding with the acid and hydroxyl OH groups of the 345THBA molecules. The hydroxyl groups of 345THBA adopt a cis–cis–trans conformation. (b) In polymorph II, one of the symmetry-independent SM molecules (shown in green) forms Thomo-II units, and makes an N—H⋯O bond with the other symmetry-independent SM molecule (shown in magenta) through its peripheral imide in an orthogonal fashion. The hydroxyl groups adopt an all trans conformation. Dotted lines indicate hydrogen bonds.

2.3. Maleimide–hydroxybenzoic acid co-crystals

2.3.1. 1:1 MM–4HBA

Crystallization of a 1:1 MM–4HBA ground mixture from methanol resulted in a 1:1 co-crystal. The structure exhibits similarity to the 1:1 SM–4HBA co-crystal in that the tapes formed by C—H⋯O-connected maleimide molecules and 4HBA carboxylic acid dimers, joined by imide–hydroxyphenyl interactions, extend into a sheet structure through O— H_hydroxyl⋯O=C_imide and multiple C—H⋯O interactions (Fig. 10). Further, akin to SM–4HBA, the MM–4HBA co-crystal features maximal intermolecular hydrogen bonding to compensate for the lack of strong imide N—H⋯O homodimers.

Figure 10 The structure of the 1:1 MM–4HBA co-crystal. Parallel tapes consisting of imide C—H⋯O-connected maleimide molecules and acid homodimers joined by imide–hydroxyphenyl heterodimers extend into a sheet through O—Hhydroxy⋯O=Cimide and multiple C—H⋯O interactions. Dotted lines indicate hydrogen bonds.

2.3.2. 1:1 MM–24DHBA

Crystallization of a 1:1 MM–24DHBA ground mixture from methanol resulted in a 1:1 co-crystal. Interestingly, the structure has no resemblance to either of the two 1:1 SM–24DHBA co-crystal polymorphs. Instead, it exhibits similarity with the MM–4HBA and SM–4HBA co-crystals, more so with the former in that both of them lack the centrosymmetric imide C—H⋯O homodimers which are characteristic of the SM–4HBA co-crystal. Overall, the co-crystal forms a sheet structure akin to MM–4HBA, sustained by imide–hydroxyphenyl and C—H⋯O interactions (Fig. 11).

Figure 11 The structure of the 1:1 MM–24DHBA co-crystal. Parallel tapes consisting of imide C—H⋯O-connected maleimide molecules and acid homodimers attached through imide–hydroxyphenyl heterodimers extend into a sheet through O—Hhydroxy⋯O=Cimide and multiple C—H⋯O interactions. Dotted lines indicate hydrogen bonds.

2.3.3. 1:3:3 MM–35DHBA–H₂O

Similar to SM–35DHBA, a co-crystal trihydrate with stoichiometry 1:3:3 MM–35DHBA–H₂O was obtained when a 1:1 MM–35DHBA ground mixture was crystallized from methanol. The structure is closely comparable with (but not entirely identical to) SM–35DHBA–H₂O, in which hexameric motifs of 35DHBA molecules make voids for succinimide N—H⋯O dimers and water molecules (Fig. 12). In this case, all of the hydroxyl groups and water molecules appear to be disordered within the planar hydrogen-bond networks. Compared with SM–35DHBA, the layers of 35DHBA molecules are aligned slightly differently, as a result of accommodating the MM molecule rather than the SM molecule within the voids.

Figure 12 The structure of the 1:3:3 MM–35DHBA–H2O co-crystal hydrate. The structure is comparable with that of SM–35DHBA–H2O. Parallel hexameric motifs formed by two sets of unique 35DHBA molecules (shown in different colours) make voids for the maleimide and water molecules. Dotted lines indicate hydrogen bonds. The disorder of the H atoms is not shown.

2.3.4. MM–34DHBA and MM–345THBA combinations

Although no crystal structures could be determined because of a lack of diffraction-quality single crystals, distinct PXRD patterns compared with their parent compounds establish these as co-crystal-forming combinations (see supporting information ).

2.4. Glutarimide–hydroxybenzoic acid co-crystals

2.4.1. 1:2 GM–4HBA

Crystallization of a 1:1 GM–4HBA ground mixture from methanol resulted in a co-crystal with 1:2 stoichiometry. The structure displays non-planar T_homo-II units formed by N—H⋯O dimers between GM molecules, and acid homodimers formed between 4HBA molecules connected through carbonyl–hydroxyl interactions (Fig. 13). The 4HBA molecules form two pairs of homodimers in which the component 4HBA molecules have different hydroxyl conformations (cis in one molecule and trans in the other, within a given pair).

Figure 13 The structure of the 1:2 GM–4HBA co-crystal. Non-planar Thomo-II units are formed by N—H⋯O dimers between symmetry-independent GM molecules (shown in different colours). Acid homodimers between independent 4HBA molecules are connected through O—Hhydroxy⋯O=Cimide interactions. Dotted lines indicate hydrogen bonds.

2.4.2. 1:1 GM–35DHBA co-crystal

Crystallization of a 1:1 GM–4HBA ground mixture from methanol resulted in a 1:1 co-crystal. The crystal structure includes T_hetero units consisting of imide–acid ring heterodimers which are propagated by hydrogen bonds between the peripheral carbonyls of GM and the meta-hydroxyl groups of 35DHBA (Fig. 14).

Figure 14 The structure of the 1:1 GM–35DHBA co-crystal. The glutarimide and 35DHBA molecules form Thetero units through imide–acid ring dimers, which propagate through meta O—Hhydroxyl⋯O=Cimide interactions. Dotted lines indicate hydrogen bonds.

2.4.3. GM–24DHBA/34DHBA/345THBA

Moragues-Bartolome et al. (2012) reported the formation of a new solid for the GM–24DHBA combination but could not produce single crystals suitable for structure determination. Similarly, we could not obtain crystal structures of these combinations, but their distinct PXRD patterns compared with their parent compounds (see supporting information ) establish them to be co-crystal-forming combinations.

2.5. Binary phase diagrams of eutectic-forming combinations

Moragues-Bartolome et al. (2012) concluded that the benzoic acid–succinimide/glutarimide combination did not form co-crystals. We corroborate this result, but in addition can demonstrate the formation of eutectic mixtures by constructing phase diagrams. The thermal behaviour of different molar compositions (1:1, 1:2, 2:1, 1:3, 3:1, 1:4, 4:1) for each of the combinations was analysed on a melting-point apparatus and the solidus–liquidus events were plotted. Based on the single invariant low melting point observed in all compositions, and the characteristic `V'-type phase diagram, co-crystal formation in any stoichiometric ratio is ruled out. The eutectic composition for each of the combinations was determined from the meeting of the solidus and liquidus points. All three cyclic imides formed eutectics with benzoic acid and 2- and 3-hydroxybenzoic acids, and the phase diagrams are given in Figs. 15–17. The structural basis for the eutectic mixtures is the possibility of finite T_homo or T_hetero units, as discussed before.

Figure 15 Binary phase diagrams of eutectic systems of (a) SM–BA, (b) SM–2HBA and (c) SM–3HBA combinations. Solidus points are shown in red and liquidus points in green.

Figure 16 Binary phase diagrams of eutectic systems of (a) MM–BA, (b) MM–2HBA and (c) MM–3HBA combinations. Solidus points are shown in red and liquidus points in green.

Figure 17 Binary phase diagrams of eutectic systems of (a) GM–BA, (b) GM–2HBA and (c) GM–3HBA combinations. Solidus points are shown in red and liquidus points in green.

3. Conclusions

We have carried out an extensive study of the supramolecular compatibility of various cyclic imide–aromatic carboxylic acid combinations in terms of the formation of co-crystals and eutectic mixtures. Several co-crystals and eutectics were obtained, in accordance with our supramolecular design schematics. It appears convincing that, in general, all the cyclic imide–hydroxybenzoic acid co-crystals manifest as per Figs. 2 and 4. However, the co-crystal architecture schematized is an ideal situation and suits only 1:1 stoichiometries, if any. The strength and conformational flexibility associated with the hydroxyl group and the crystallization milieu factors (solvent, temperature, supersaturation etc.) facilitate co-crystal formation in different architectures (polymorphic arrangements), with different conformers (multiple stoichiometry), and sometimes including water of crystallization (Thakuria et al., 2012). Earlier studies from our group have shown that the relative differences in the propensity to form supramolecular synthons and in the induction strength complementarity of hydrogen-bonding functional groups guide the formation of co-crystals and eutectics in a mutually exclusive manner for a given combination (Cherukuvada & Row, 2014; Prasad et al., 2014). In this work, we have provided a rationale for their formation in the systems studied on the basis of an additional functional group (in this case hydroxyl) and its geometric disposition and resultant supramolecular effect in different combinations. The observation of a sharp melting point lower than those of the individual components, and the coexistence of individual components (as per PXRD patterns), in the medicinally relevant systems studied here strengthens the prospects of eutectics for pharmaceutical applications. This work improves our understanding of the requisites for selective co-crystal or eutectic formation for a combination with extensive hydrogen-bonding prospects.

Supporting information

Computing details

Data collection: CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) for SM-4HBA, SM-24DHBA, SM-34DHBA, MM-4HBA, GM-4HBA, GM-35DHBA; CrysAlis PRO CCD (Oxford Diffraction, 2009) for SM-345THBAI; CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) for SM-345THBAII; CrysAlis PRO, Agilent Technologies, Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET) (compiled Dec 3 2012,18:21:49) for SM-35DHBA, MM-35DHBA; CrysAlis PRO, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) for MM-24DHBA. Cell refinement: CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) for SM-4HBA, SM-24DHBA, SM-34DHBA, MM-4HBA, GM-4HBA, GM-35DHBA; CrysAlis PRO CCD (Oxford Diffraction, 2009) for SM-345THBAI; CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) for SM-345THBAII; CrysAlis PRO, Agilent Technologies, Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET) (compiled Dec 3 2012,18:21:49) for SM-35DHBA, MM-35DHBA; CrysAlis PRO, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) for MM-24DHBA. Data reduction: CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) for SM-4HBA, SM-24DHBA, SM-34DHBA, MM-4HBA, GM-4HBA, GM-35DHBA; CrysAlis PRO RED (Oxford Diffraction, 2009) for SM-345THBAI; CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) for SM-345THBAII; CrysAlis PRO, Agilent Technologies, Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET) (compiled Dec 3 2012,18:21:49) for SM-35DHBA, MM-35DHBA; CrysAlis PRO, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) for MM-24DHBA. Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for SM-345THBAI. Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for SM-345THBAI; SHELXL2013 (Sheldrick, 2013) for SM-35DHBA, MM-35DHBA. Molecular graphics: ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1993) for SM-345THBAI. Software used to prepare material for publication: PLATON (Spek, 2003) for SM-4HBA, SM-24DHBA, SM-34DHBA, SM-345THBAII, MM-4HBA, MM-24DHBA, GM-4HBA, GM-35DHBA; WinGX (Farrugia, 1999) for SM-345THBAI.

(SM-4HBA)

Crystal data

C7H6O3·C4H5NO2	Z = 2
Mr = 237.21	F(000) = 248
Triclinic, P1	Dx = 1.459 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5133 (3) Å	Cell parameters from 8365 reflections
b = 8.1853 (5) Å	θ = 3.4–29.9°
c = 11.4965 (6) Å	µ = 0.12 mm^−1
α = 103.458 (5)°	T = 100 K
β = 93.925 (4)°	Block, colourless
γ = 113.018 (5)°	0.43 × 0.24 × 0.23 mm
V = 539.85 (6) Å^3

Data collection

Xcalibur, Eos, Nova diffractometer	Rint = 0.035
Mirror monochromator	θmax = 30.2°, θmin = 2.8°
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→9
Tmin = 0.843, Tmax = 1.000	k = −11→11
13046 measured reflections	l = −16→15
1903 independent 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0461P)^2 + 0.1643P] where P = (Fo^2 + 2Fc^2)/3
1903 reflections	(Δ/σ)max < 0.001
166 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
C1	0.08575 (19)	0.07710 (15)	0.85791 (10)	0.0154 (3)
C2	0.15232 (19)	0.13804 (15)	0.74955 (10)	0.0154 (3)
C7	−0.00327 (19)	0.16678 (15)	0.67570 (10)	0.0161 (3)
H7	−0.1447	0.1484	0.6963	0.019*
C6	0.05023 (19)	0.22189 (16)	0.57288 (10)	0.0164 (3)
H6	−0.0541	0.2414	0.5249	0.020*
C5	0.26237 (19)	0.24835 (15)	0.54103 (10)	0.0151 (3)
C4	0.4203 (2)	0.22114 (16)	0.61406 (11)	0.0176 (3)
H4	0.5616	0.2396	0.5933	0.021*
C3	0.3650 (2)	0.16646 (16)	0.71759 (10)	0.0175 (3)
H3	0.4699	0.1485	0.7662	0.021*
C8	0.0155 (2)	0.38221 (16)	0.15958 (11)	0.0171 (3)
C9	−0.2032 (2)	0.37489 (17)	0.09818 (11)	0.0189 (3)
H9A	−0.2653	0.2753	0.0230	0.023*
H9B	−0.1773	0.4908	0.0803	0.023*
C10	−0.3636 (2)	0.34070 (17)	0.18976 (11)	0.0199 (3)
H10A	−0.4144	0.4388	0.2106	0.024*
H10B	−0.4951	0.2235	0.1569	0.024*
C11	−0.22631 (19)	0.33794 (15)	0.29932 (11)	0.0161 (3)
N1	−0.01497 (17)	0.36098 (14)	0.27538 (9)	0.0166 (2)
O2	0.24039 (14)	0.05279 (12)	0.92336 (7)	0.0194 (2)
O1	−0.10420 (14)	0.04944 (11)	0.88444 (7)	0.0192 (2)
O3	0.30534 (14)	0.29955 (12)	0.43755 (7)	0.0181 (2)
O4	0.18793 (14)	0.40198 (13)	0.11986 (8)	0.0249 (2)
O5	−0.28862 (14)	0.31711 (12)	0.39538 (8)	0.0220 (2)
H2O	0.181 (3)	0.017 (3)	0.9919 (19)	0.059 (6)*
H3O	0.438 (3)	0.304 (2)	0.4229 (16)	0.045 (5)*
H1N	0.085 (3)	0.354 (2)	0.3261 (15)	0.030 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0167 (6)	0.0134 (5)	0.0155 (6)	0.0062 (5)	0.0029 (4)	0.0028 (4)
C2	0.0169 (6)	0.0135 (5)	0.0154 (6)	0.0060 (4)	0.0035 (4)	0.0037 (4)
C7	0.0136 (6)	0.0175 (6)	0.0185 (6)	0.0073 (5)	0.0058 (4)	0.0057 (5)
C6	0.0150 (6)	0.0198 (6)	0.0167 (6)	0.0090 (5)	0.0022 (4)	0.0063 (5)
C5	0.0174 (6)	0.0148 (5)	0.0132 (5)	0.0063 (5)	0.0042 (4)	0.0044 (4)
C4	0.0143 (6)	0.0231 (6)	0.0187 (6)	0.0092 (5)	0.0063 (4)	0.0085 (5)
C3	0.0166 (6)	0.0212 (6)	0.0175 (6)	0.0098 (5)	0.0027 (4)	0.0075 (5)
C8	0.0188 (6)	0.0180 (6)	0.0173 (6)	0.0096 (5)	0.0048 (5)	0.0063 (4)
C9	0.0200 (6)	0.0248 (6)	0.0178 (6)	0.0137 (5)	0.0037 (5)	0.0087 (5)
C10	0.0165 (6)	0.0257 (6)	0.0202 (6)	0.0108 (5)	0.0026 (5)	0.0082 (5)
C11	0.0159 (6)	0.0151 (5)	0.0196 (6)	0.0077 (5)	0.0048 (5)	0.0062 (4)
N1	0.0147 (5)	0.0230 (5)	0.0167 (5)	0.0106 (4)	0.0037 (4)	0.0087 (4)
O2	0.0197 (4)	0.0268 (5)	0.0166 (4)	0.0121 (4)	0.0052 (3)	0.0106 (4)
O1	0.0167 (4)	0.0259 (5)	0.0177 (4)	0.0092 (4)	0.0063 (3)	0.0098 (3)
O3	0.0155 (4)	0.0282 (5)	0.0162 (4)	0.0111 (4)	0.0068 (3)	0.0120 (3)
O4	0.0204 (5)	0.0390 (5)	0.0241 (5)	0.0170 (4)	0.0111 (4)	0.0151 (4)
O5	0.0202 (4)	0.0334 (5)	0.0218 (5)	0.0156 (4)	0.0100 (3)	0.0156 (4)

Geometric parameters (Å, º)

C1—O1	1.2409 (14)	C4—C3	1.3882 (17)
C1—O2	1.3202 (14)	C8—O4	1.2075 (15)
C1—C2	1.4774 (16)	C8—N1	1.3996 (15)
C2—C7	1.4017 (17)	C8—C9	1.5189 (16)
C2—C3	1.4017 (17)	C9—C10	1.5290 (16)
C7—C6	1.3799 (16)	C10—C11	1.5038 (16)
C6—C5	1.4008 (16)	C11—O5	1.2281 (15)
C5—O3	1.3620 (14)	C11—N1	1.3708 (15)
C5—C4	1.4000 (17)
O1—C1—O2	122.58 (11)	C3—C4—C5	119.71 (11)
O1—C1—C2	121.77 (10)	C4—C3—C2	120.57 (11)
O2—C1—C2	115.64 (10)	O4—C8—N1	124.10 (11)
C7—C2—C3	118.95 (11)	O4—C8—C9	128.45 (11)
C7—C2—C1	118.84 (10)	N1—C8—C9	107.45 (10)
C3—C2—C1	122.21 (10)	C8—C9—C10	105.04 (9)
C6—C7—C2	120.97 (11)	C11—C10—C9	105.13 (9)
C7—C6—C5	119.69 (10)	O5—C11—N1	124.12 (11)
O3—C5—C4	122.50 (10)	O5—C11—C10	126.99 (11)
O3—C5—C6	117.40 (10)	N1—C11—C10	108.89 (10)
C4—C5—C6	120.10 (11)	C11—N1—C8	113.45 (10)
O1—C1—C2—C7	0.59 (16)	C7—C2—C3—C4	−0.37 (17)
O2—C1—C2—C7	−179.97 (10)	C1—C2—C3—C4	179.05 (10)
O1—C1—C2—C3	−178.83 (10)	O4—C8—C9—C10	178.00 (12)
O2—C1—C2—C3	0.61 (16)	N1—C8—C9—C10	−1.86 (12)
C3—C2—C7—C6	0.10 (17)	C8—C9—C10—C11	2.17 (12)
C1—C2—C7—C6	−179.34 (10)	C9—C10—C11—O5	178.82 (11)
C2—C7—C6—C5	0.47 (17)	C9—C10—C11—N1	−1.79 (13)
C7—C6—C5—O3	178.86 (10)	O5—C11—N1—C8	−179.94 (10)
C7—C6—C5—C4	−0.77 (17)	C10—C11—N1—C8	0.65 (13)
O3—C5—C4—C3	−179.11 (10)	O4—C8—N1—C11	−179.07 (11)
C6—C5—C4—C3	0.50 (17)	C9—C8—N1—C11	0.81 (13)
C5—C4—C3—C2	0.08 (17)

(SM-24DHBA)

Crystal data

C7H6O4·C4H5NO2	Z = 2
Mr = 253.21	F(000) = 264
Triclinic, P1	Dx = 1.579 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.7358 (8) Å	Cell parameters from 2754 reflections
b = 6.9119 (8) Å	θ = 3.4–29.8°
c = 12.3937 (9) Å	µ = 0.13 mm^−1
α = 74.468 (9)°	T = 100 K
β = 85.298 (8)°	Block, colourless
γ = 73.28 (1)°	0.35 × 0.29 × 0.10 mm
V = 532.43 (10) Å^3

Data collection

Xcalibur, Eos, Nova diffractometer	1690 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.026
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θmax = 25.0°, θmin = 3.2°
Tmin = 0.755, Tmax = 1.000	h = −8→8
4016 measured reflections	k = −8→6
1861 independent reflections	l = −14→13

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.147	w = 1/[σ^2(Fo^2) + (0.0365P)^2 + 1.0119P] where P = (Fo^2 + 2Fc^2)/3
S = 1.26	(Δ/σ)max < 0.001
1861 reflections	Δρmax = 0.55 e Å^−3
179 parameters	Δρmin = −0.37 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.4868 (4)	0.3357 (4)	0.9082 (2)	0.0164 (6)
C2	0.4839 (4)	0.4529 (4)	0.7903 (2)	0.0158 (6)
C7	0.6636 (4)	0.5087 (4)	0.7433 (2)	0.0156 (6)
C6	0.6622 (4)	0.6255 (4)	0.6330 (2)	0.0164 (6)
H6	0.7806	0.6627	0.6018	0.020*
C5	0.4856 (4)	0.6862 (4)	0.5699 (2)	0.0154 (6)
C4	0.3066 (4)	0.6303 (4)	0.6141 (2)	0.0164 (6)
H4	0.1888	0.6708	0.5703	0.020*
C3	0.3067 (4)	0.5146 (4)	0.7231 (2)	0.0151 (6)
H7	0.1880	0.4766	0.7529	0.018*
C8	0.1714 (4)	0.0580 (4)	0.1998 (2)	0.0157 (6)
C9	−0.0237 (4)	0.1237 (4)	0.1334 (2)	0.0180 (6)
H9A	0.0015	0.0761	0.0654	0.022*
H9B	−0.0794	0.2745	0.1137	0.022*
C10	−0.1733 (4)	0.0187 (4)	0.2119 (2)	0.0190 (6)
H10A	−0.3033	0.1205	0.2199	0.023*
H10B	−0.2012	−0.0889	0.1837	0.023*
C11	−0.0603 (4)	−0.0744 (4)	0.3217 (2)	0.0175 (6)
N1	0.1352 (4)	−0.0449 (4)	0.3068 (2)	0.0166 (5)
O1	0.6438 (3)	0.2770 (3)	0.96707 (16)	0.0209 (5)
O2	0.3116 (3)	0.2956 (3)	0.94891 (16)	0.0213 (5)
O4	0.8403 (3)	0.4514 (3)	0.80187 (16)	0.0204 (5)
O3	0.4780 (3)	0.8045 (3)	0.46181 (16)	0.0191 (5)
O5	0.3385 (3)	0.0884 (3)	0.16640 (16)	0.0194 (5)
O6	−0.1252 (3)	−0.1641 (3)	0.41058 (17)	0.0242 (5)
H1N	0.224 (6)	−0.086 (5)	0.355 (3)	0.020 (9)*
H2O	0.318 (7)	0.227 (6)	1.0147 (14)	0.058 (14)*
H4O	0.811 (8)	0.394 (7)	0.8659 (17)	0.070 (16)*
H3O	0.618 (6)	0.815 (6)	0.442 (3)	0.035 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0180 (14)	0.0158 (13)	0.0144 (13)	−0.0051 (11)	−0.0023 (11)	−0.0009 (10)
C2	0.0205 (14)	0.0132 (12)	0.0132 (13)	−0.0060 (11)	0.0018 (11)	−0.0018 (10)
C7	0.0161 (13)	0.0157 (13)	0.0145 (13)	−0.0062 (10)	−0.0015 (10)	−0.0006 (10)
C6	0.0175 (13)	0.0164 (13)	0.0149 (13)	−0.0090 (11)	0.0046 (11)	−0.0002 (10)
C5	0.0239 (14)	0.0113 (12)	0.0101 (12)	−0.0054 (11)	−0.0003 (11)	−0.0008 (10)
C4	0.0182 (14)	0.0174 (13)	0.0128 (13)	−0.0053 (11)	−0.0012 (11)	−0.0015 (10)
C3	0.0190 (14)	0.0148 (12)	0.0119 (13)	−0.0081 (10)	0.0019 (10)	−0.0013 (10)
C8	0.0199 (14)	0.0136 (12)	0.0134 (13)	−0.0060 (11)	0.0028 (11)	−0.0022 (10)
C9	0.0187 (14)	0.0195 (14)	0.0148 (13)	−0.0048 (11)	−0.0024 (11)	−0.0023 (11)
C10	0.0192 (14)	0.0172 (13)	0.0200 (14)	−0.0063 (11)	−0.0018 (11)	−0.0021 (11)
C11	0.0202 (14)	0.0148 (13)	0.0158 (14)	−0.0050 (11)	−0.0023 (11)	−0.0005 (10)
N1	0.0167 (12)	0.0186 (12)	0.0118 (12)	−0.0063 (9)	−0.0011 (10)	0.0025 (9)
O1	0.0188 (10)	0.0248 (11)	0.0155 (10)	−0.0072 (8)	−0.0031 (8)	0.0031 (8)
O2	0.0217 (11)	0.0271 (11)	0.0124 (10)	−0.0103 (9)	−0.0002 (8)	0.0034 (8)
O4	0.0156 (10)	0.0276 (11)	0.0140 (10)	−0.0080 (8)	−0.0030 (8)	0.0042 (8)
O3	0.0220 (11)	0.0210 (10)	0.0125 (9)	−0.0097 (8)	−0.0005 (8)	0.0029 (8)
O5	0.0196 (10)	0.0234 (10)	0.0148 (10)	−0.0103 (8)	−0.0011 (8)	0.0009 (8)
O6	0.0254 (11)	0.0270 (11)	0.0165 (10)	−0.0126 (9)	0.0027 (8)	0.0054 (8)

Geometric parameters (Å, º)

C1—O1	1.239 (3)	C5—C4	1.397 (4)
C1—O2	1.319 (3)	C4—C3	1.373 (4)
C1—C2	1.468 (4)	C8—O5	1.223 (3)
C2—C3	1.407 (4)	C8—N1	1.366 (3)
C2—C7	1.409 (4)	C8—C9	1.498 (4)
C7—O4	1.348 (3)	C9—C10	1.539 (4)
C7—C6	1.388 (4)	C10—C11	1.505 (4)
C6—C5	1.376 (4)	C11—O6	1.224 (3)
C5—O3	1.366 (3)	C11—N1	1.380 (4)
O1—C1—O2	121.3 (2)	C6—C5—C4	121.3 (2)
O1—C1—C2	122.5 (3)	C3—C4—C5	119.2 (3)
O2—C1—C2	116.1 (2)	C4—C3—C2	120.9 (2)
C3—C2—C7	118.9 (2)	O5—C8—N1	124.0 (3)
C3—C2—C1	122.3 (2)	O5—C8—C9	127.0 (2)
C7—C2—C1	118.8 (2)	N1—C8—C9	109.0 (2)
O4—C7—C6	118.0 (2)	C8—C9—C10	104.5 (2)
O4—C7—C2	122.2 (2)	C11—C10—C9	104.2 (2)
C6—C7—C2	119.9 (2)	O6—C11—N1	124.2 (3)
C5—C6—C7	119.9 (2)	O6—C11—C10	127.2 (3)
O3—C5—C6	121.4 (2)	N1—C11—C10	108.6 (2)
O3—C5—C4	117.4 (2)	C8—N1—C11	113.1 (2)
O1—C1—C2—C3	178.4 (3)	C6—C5—C4—C3	0.8 (4)
O2—C1—C2—C3	−1.7 (4)	C5—C4—C3—C2	0.2 (4)
O1—C1—C2—C7	−2.8 (4)	C7—C2—C3—C4	−1.0 (4)
O2—C1—C2—C7	177.2 (2)	C1—C2—C3—C4	177.8 (2)
C3—C2—C7—O4	−178.6 (2)	O5—C8—C9—C10	172.3 (3)
C1—C2—C7—O4	2.5 (4)	N1—C8—C9—C10	−7.6 (3)
C3—C2—C7—C6	1.0 (4)	C8—C9—C10—C11	7.3 (3)
C1—C2—C7—C6	−177.9 (2)	C9—C10—C11—O6	175.9 (3)
O4—C7—C6—C5	179.6 (2)	C9—C10—C11—N1	−4.8 (3)
C2—C7—C6—C5	0.0 (4)	O5—C8—N1—C11	−175.0 (3)
C7—C6—C5—O3	178.8 (2)	C9—C8—N1—C11	4.9 (3)
C7—C6—C5—C4	−0.9 (4)	O6—C11—N1—C8	179.5 (3)
O3—C5—C4—C3	−178.8 (2)	C10—C11—N1—C8	0.1 (3)

(SM-34DHBA)

Crystal data

2(C7H6O4)·C4H5NO2	F(000) = 848
Mr = 407.33	Dx = 1.577 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4761 reflections
a = 6.7323 (2) Å	θ = 3.1–29.9°
b = 12.1142 (5) Å	µ = 0.13 mm^−1
c = 21.2077 (8) Å	T = 100 K
β = 97.146 (3)°	Block, colourless
V = 1716.19 (11) Å^3	0.33 × 0.15 × 0.11 mm
Z = 4

Data collection

Xcalibur, Eos, Nova diffractometer	2818 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.040
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET) (compiled Feb 1 2013,16:14:44) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	θmax = 26.0°, θmin = 2.6°
Tmin = 0.880, Tmax = 1.000	h = −8→8
10777 measured reflections	k = −14→13
3365 independent reflections	l = −25→26

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.044	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.035P)^2 + 0.5769P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3365 reflections	Δρmax = 0.27 e Å^−3
290 parameters	Δρmin = −0.22 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.4685 (2)	0.76778 (14)	0.13733 (8)	0.0159 (4)
C2	0.6615 (2)	0.70887 (14)	0.14576 (8)	0.0158 (4)
C3	0.7557 (3)	0.68234 (15)	0.20625 (8)	0.0169 (4)
H3	0.6986	0.7044	0.2420	0.020*
C4	0.9328 (3)	0.62371 (15)	0.21354 (9)	0.0186 (4)
H4	0.9936	0.6058	0.2540	0.022*
C5	1.0206 (2)	0.59129 (15)	0.16052 (8)	0.0163 (4)
C6	0.9297 (3)	0.62091 (15)	0.10000 (8)	0.0165 (4)
C7	0.7513 (3)	0.67771 (15)	0.09250 (8)	0.0174 (4)
H7	0.6904	0.6954	0.0520	0.021*
C8	−0.0216 (3)	0.93239 (15)	0.12621 (8)	0.0161 (4)
C9	−0.2137 (2)	0.99223 (14)	0.12435 (8)	0.0154 (4)
C10	−0.3007 (2)	1.04901 (14)	0.07059 (8)	0.0152 (4)
H10	−0.2382	1.0499	0.0339	0.018*
C11	−0.4801 (3)	1.10383 (15)	0.07225 (8)	0.0157 (4)
C12	−0.5755 (2)	1.10051 (15)	0.12748 (8)	0.0161 (4)
C13	−0.4885 (3)	1.04325 (15)	0.18033 (8)	0.0178 (4)
H13	−0.5520	1.0407	0.2168	0.021*
C14	−0.3080 (2)	0.98998 (15)	0.17906 (8)	0.0166 (4)
H14	−0.2493	0.9525	0.2149	0.020*
C15	0.1838 (3)	0.81744 (16)	0.34921 (8)	0.0199 (4)
H15A	0.0793	0.8493	0.3191	0.024*
H15B	0.1947	0.7393	0.3402	0.024*
C16	0.1407 (3)	0.83545 (15)	0.41635 (9)	0.0192 (4)
C17	0.4443 (3)	0.92048 (15)	0.41182 (9)	0.0181 (4)
C18	0.3845 (3)	0.87644 (16)	0.34617 (8)	0.0204 (4)
H18A	0.4843	0.8252	0.3344	0.024*
H18B	0.3692	0.9361	0.3154	0.024*
N1	0.2959 (2)	0.89362 (13)	0.44855 (7)	0.0187 (4)
O1	0.38957 (17)	0.80267 (11)	0.08513 (6)	0.0195 (3)
O2	0.38602 (18)	0.77968 (11)	0.18979 (6)	0.0195 (3)
O3	1.19142 (18)	0.53090 (11)	0.16778 (6)	0.0215 (3)
O4	1.02518 (19)	0.58628 (12)	0.05054 (6)	0.0247 (3)
O5	0.06585 (18)	0.89639 (11)	0.17626 (6)	0.0202 (3)
O6	0.04641 (19)	0.91969 (11)	0.07084 (6)	0.0216 (3)
O7	−0.57499 (19)	1.16596 (11)	0.02385 (6)	0.0216 (3)
O8	−0.75181 (18)	1.15372 (11)	0.13133 (6)	0.0213 (3)
O9	−0.00706 (18)	0.80537 (11)	0.43979 (6)	0.0254 (3)
O10	0.59488 (18)	0.97186 (11)	0.43126 (6)	0.0237 (3)
H1N	0.300 (3)	0.9184 (16)	0.4864 (9)	0.019 (5)*
H2O	0.266 (4)	0.822 (2)	0.1810 (13)	0.066 (8)*
H3O	1.225 (3)	0.519 (2)	0.1302 (11)	0.046 (7)*
H4O	0.983 (4)	0.627 (2)	0.0116 (12)	0.059 (8)*
H6O	0.167 (4)	0.881 (2)	0.0760 (11)	0.051 (7)*
H7O	−0.512 (3)	1.1660 (17)	−0.0093 (10)	0.033 (6)*
H8O	−0.792 (3)	1.1900 (19)	0.0954 (11)	0.037 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0155 (9)	0.0132 (9)	0.0197 (9)	−0.0021 (7)	0.0045 (7)	−0.0011 (8)
C2	0.0157 (9)	0.0132 (9)	0.0191 (9)	−0.0004 (7)	0.0045 (7)	0.0005 (8)
C3	0.0189 (9)	0.0162 (9)	0.0167 (9)	0.0002 (7)	0.0063 (7)	−0.0012 (8)
C4	0.0203 (9)	0.0188 (10)	0.0164 (9)	0.0014 (8)	0.0014 (7)	0.0012 (8)
C5	0.0140 (8)	0.0138 (9)	0.0211 (9)	0.0022 (7)	0.0021 (7)	0.0009 (8)
C6	0.0166 (9)	0.0164 (9)	0.0176 (9)	0.0019 (7)	0.0059 (7)	−0.0002 (8)
C7	0.0170 (9)	0.0189 (10)	0.0157 (9)	0.0015 (7)	−0.0001 (7)	0.0024 (8)
C8	0.0159 (9)	0.0161 (9)	0.0166 (9)	−0.0017 (7)	0.0030 (7)	−0.0008 (8)
C9	0.0145 (8)	0.0142 (9)	0.0173 (9)	−0.0007 (7)	0.0012 (7)	−0.0030 (8)
C10	0.0150 (8)	0.0177 (9)	0.0139 (9)	−0.0011 (7)	0.0049 (7)	−0.0014 (8)
C11	0.0172 (9)	0.0146 (9)	0.0148 (9)	−0.0002 (7)	−0.0005 (7)	−0.0001 (8)
C12	0.0138 (8)	0.0157 (9)	0.0192 (9)	0.0011 (7)	0.0033 (7)	−0.0028 (8)
C13	0.0178 (9)	0.0209 (10)	0.0155 (9)	0.0000 (7)	0.0053 (7)	−0.0006 (8)
C14	0.0191 (9)	0.0156 (9)	0.0147 (9)	−0.0001 (7)	0.0010 (7)	0.0008 (8)
C15	0.0203 (9)	0.0196 (10)	0.0192 (9)	−0.0011 (8)	−0.0002 (7)	−0.0016 (8)
C16	0.0189 (9)	0.0171 (10)	0.0216 (10)	−0.0010 (8)	0.0025 (8)	0.0002 (8)
C17	0.0177 (9)	0.0168 (9)	0.0207 (9)	0.0009 (8)	0.0058 (7)	0.0016 (8)
C18	0.0223 (9)	0.0224 (10)	0.0171 (9)	−0.0002 (8)	0.0051 (8)	0.0010 (8)
N1	0.0178 (8)	0.0235 (9)	0.0155 (8)	−0.0053 (7)	0.0050 (6)	−0.0028 (7)
O1	0.0168 (6)	0.0251 (7)	0.0166 (7)	0.0059 (5)	0.0029 (5)	0.0018 (6)
O2	0.0174 (6)	0.0231 (7)	0.0191 (7)	0.0057 (6)	0.0069 (5)	0.0026 (6)
O3	0.0184 (6)	0.0287 (8)	0.0178 (7)	0.0097 (6)	0.0033 (5)	−0.0005 (6)
O4	0.0243 (7)	0.0327 (8)	0.0182 (7)	0.0127 (6)	0.0072 (6)	0.0018 (7)
O5	0.0172 (6)	0.0249 (7)	0.0187 (7)	0.0055 (5)	0.0030 (5)	0.0015 (6)
O6	0.0179 (6)	0.0290 (8)	0.0190 (7)	0.0079 (6)	0.0064 (5)	0.0002 (6)
O7	0.0220 (7)	0.0271 (8)	0.0164 (7)	0.0079 (6)	0.0056 (6)	0.0048 (6)
O8	0.0171 (6)	0.0283 (8)	0.0191 (7)	0.0094 (6)	0.0048 (5)	0.0050 (6)
O9	0.0210 (7)	0.0304 (8)	0.0260 (7)	−0.0092 (6)	0.0077 (6)	−0.0064 (6)
O10	0.0178 (7)	0.0299 (8)	0.0243 (7)	−0.0077 (6)	0.0058 (5)	−0.0037 (6)

Geometric parameters (Å, º)

C1—O1	1.241 (2)	C9—C10	1.396 (2)
C1—O2	1.312 (2)	C10—C11	1.383 (2)
C1—C2	1.474 (2)	C11—O7	1.366 (2)
C2—C3	1.396 (3)	C11—C12	1.405 (2)
C2—C7	1.398 (2)	C12—O8	1.362 (2)
C3—C4	1.380 (2)	C12—C13	1.385 (3)
C4—C5	1.391 (2)	C13—C14	1.379 (2)
C5—O3	1.355 (2)	C15—C16	1.504 (2)
C5—C6	1.398 (2)	C15—C18	1.537 (2)
C6—O4	1.3627 (19)	C16—O9	1.222 (2)
C6—C7	1.376 (2)	C16—N1	1.370 (2)
C8—O5	1.228 (2)	C17—O10	1.217 (2)
C8—O6	1.322 (2)	C17—N1	1.380 (2)
C8—C9	1.479 (2)	C17—C18	1.499 (3)
C9—C14	1.391 (2)
O1—C1—O2	122.69 (15)	C10—C9—C8	122.66 (15)
O1—C1—C2	123.10 (15)	C11—C10—C9	119.64 (15)
O2—C1—C2	114.21 (16)	O7—C11—C10	125.02 (15)
C3—C2—C7	119.20 (16)	O7—C11—C12	115.03 (15)
C3—C2—C1	121.05 (15)	C10—C11—C12	119.93 (16)
C7—C2—C1	119.75 (16)	O8—C12—C13	118.19 (15)
C4—C3—C2	120.59 (15)	O8—C12—C11	121.91 (16)
C3—C4—C5	120.20 (17)	C13—C12—C11	119.89 (15)
O3—C5—C4	120.04 (16)	C14—C13—C12	120.23 (16)
O3—C5—C6	120.73 (15)	C13—C14—C9	120.14 (17)
C4—C5—C6	119.23 (16)	C16—C15—C18	104.27 (15)
O4—C6—C7	123.60 (16)	O9—C16—N1	124.03 (16)
O4—C6—C5	115.66 (15)	O9—C16—C15	127.20 (17)
C7—C6—C5	120.69 (15)	N1—C16—C15	108.76 (14)
C6—C7—C2	120.04 (17)	O10—C17—N1	124.08 (17)
O5—C8—O6	123.00 (16)	O10—C17—C18	127.80 (15)
O5—C8—C9	121.40 (15)	N1—C17—C18	108.12 (15)
O6—C8—C9	115.60 (16)	C17—C18—C15	105.20 (14)
C14—C9—C10	120.16 (16)	C16—N1—C17	113.62 (15)
C14—C9—C8	117.18 (16)
O1—C1—C2—C3	172.54 (17)	C8—C9—C10—C11	−179.60 (16)
O2—C1—C2—C3	−7.9 (2)	C9—C10—C11—O7	176.99 (16)
O1—C1—C2—C7	−8.2 (3)	C9—C10—C11—C12	−1.1 (3)
O2—C1—C2—C7	171.37 (16)	O7—C11—C12—O8	1.4 (2)
C7—C2—C3—C4	−1.6 (3)	C10—C11—C12—O8	179.68 (16)
C1—C2—C3—C4	177.65 (16)	O7—C11—C12—C13	−177.65 (16)
C2—C3—C4—C5	0.7 (3)	C10—C11—C12—C13	0.6 (3)
C3—C4—C5—O3	−178.06 (16)	O8—C12—C13—C14	−178.71 (16)
C3—C4—C5—C6	1.4 (3)	C11—C12—C13—C14	0.4 (3)
O3—C5—C6—O4	−0.7 (2)	C12—C13—C14—C9	−0.9 (3)
C4—C5—C6—O4	179.84 (16)	C10—C9—C14—C13	0.4 (3)
O3—C5—C6—C7	176.90 (16)	C8—C9—C14—C13	−179.40 (16)
C4—C5—C6—C7	−2.6 (3)	C18—C15—C16—O9	177.86 (18)
O4—C6—C7—C2	179.03 (17)	C18—C15—C16—N1	−1.5 (2)
C5—C6—C7—C2	1.6 (3)	O10—C17—C18—C15	179.07 (18)
C3—C2—C7—C6	0.4 (3)	N1—C17—C18—C15	−1.4 (2)
C1—C2—C7—C6	−178.81 (16)	C16—C15—C18—C17	1.71 (19)
O5—C8—C9—C14	−10.6 (3)	O9—C16—N1—C17	−178.68 (18)
O6—C8—C9—C14	168.66 (16)	C15—C16—N1—C17	0.7 (2)
O5—C8—C9—C10	169.60 (17)	O10—C17—N1—C16	−179.97 (17)
O6—C8—C9—C10	−11.1 (2)	C18—C17—N1—C16	0.4 (2)
C14—C9—C10—C11	0.6 (3)

(SM-345THBAI)

Crystal data

C7H6O5·2(C4H5NO2)	Z = 4
Mr = 368.30	F(000) = 768
Orthorhombic, P212121	Dx = 1.571 Mg m^−3
Hall symbol: P 2ac 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 7.0213 (3) Å	µ = 0.13 mm^−1
b = 8.8214 (4) Å	T = 130 K
c = 25.1416 (12) Å	Needle, colourless
V = 1557.21 (12) Å^3	0.24 × 0.22 × 0.22 mm

Data collection

Oxford Xcalibur,Eos(Nova) CCD detector diffractometer	2707 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2504 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan CrysAlis RED (Oxford Diffraction,2009)	h = −8→8
Tmin = 0.969, Tmax = 0.974	k = −10→10
8817 measured reflections	l = −29→29

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0411P)^2 + 0.3109P] where P = (Fo^2 + 2Fc^2)/3
2996 reflections	(Δ/σ)max < 0.001
259 parameters	Δρmax = 0.15 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
C1	0.6257 (4)	0.6065 (3)	0.16074 (12)	0.0223 (6)
C2	0.5509 (4)	0.7513 (3)	0.13873 (12)	0.0209 (6)
C3	0.5294 (4)	0.7680 (3)	0.08363 (12)	0.0216 (6)
H3	0.5661	0.6886	0.0603	0.026*
C4	0.4543 (4)	0.9015 (3)	0.06350 (11)	0.0212 (6)
C5	0.4023 (4)	1.0186 (3)	0.09735 (12)	0.0210 (6)
C6	0.4229 (4)	1.0007 (3)	0.15270 (12)	0.0220 (6)
C7	0.4981 (4)	0.8683 (3)	0.17280 (12)	0.0224 (6)
H7	0.5141	0.8568	0.2101	0.027*
C8	0.0785 (4)	0.7070 (3)	0.19000 (12)	0.0217 (6)
C9	0.1375 (5)	0.5951 (3)	0.23168 (12)	0.0268 (7)
H9A	0.0328	0.5773	0.2573	0.032*
H9B	0.2506	0.6320	0.2513	0.032*
C10	0.1842 (5)	0.4503 (3)	0.20119 (12)	0.0270 (7)
H10A	0.3164	0.4173	0.2085	0.032*
H10B	0.0960	0.3676	0.2112	0.032*
C11	0.1604 (4)	0.4914 (3)	0.14361 (12)	0.0222 (6)
C12	−0.0584 (4)	0.9525 (3)	0.05917 (12)	0.0221 (6)
C13	−0.1106 (5)	1.0672 (3)	0.01756 (13)	0.0279 (7)
H13A	−0.2131	1.0281	−0.0057	0.033*
H13B	0.0012	1.0932	−0.0046	0.033*
C14	−0.1790 (5)	1.2053 (3)	0.04908 (12)	0.0278 (7)
H14A	−0.1024	1.2960	0.0401	0.033*
H14B	−0.3146	1.2269	0.0415	0.033*
C15	−0.1520 (4)	1.1621 (3)	0.10662 (12)	0.0227 (6)
N1	0.0951 (4)	0.6384 (3)	0.14103 (10)	0.0221 (6)
N2	−0.0814 (4)	1.0162 (3)	0.10858 (10)	0.0222 (6)
O1	0.6475 (3)	0.5817 (2)	0.20822 (9)	0.0304 (5)
O2	0.6653 (3)	0.5055 (2)	0.12357 (9)	0.0294 (5)
O3	0.4285 (3)	0.9259 (2)	0.01020 (8)	0.0277 (5)
O4	0.3309 (3)	1.1469 (2)	0.07485 (8)	0.0258 (5)
O5	0.3622 (3)	1.1207 (2)	0.18242 (9)	0.0283 (5)
O6	0.1904 (3)	0.4127 (2)	0.10476 (9)	0.0299 (5)
O7	0.0230 (3)	0.8369 (2)	0.19628 (9)	0.0276 (5)
O8	−0.0026 (3)	0.8226 (2)	0.05214 (8)	0.0256 (5)
O9	−0.1864 (3)	1.2368 (2)	0.14620 (9)	0.0283 (5)
H1N	0.069 (6)	0.687 (4)	0.1118 (17)	0.057 (13)*
H2N	−0.051 (7)	0.965 (5)	0.1414 (19)	0.078 (15)*
H2O	0.711 (6)	0.419 (5)	0.1397 (19)	0.071 (14)*
H3O	0.453 (6)	0.834 (4)	−0.0057 (14)	0.041 (11)*
H4O	0.300 (6)	1.225 (5)	0.0992 (18)	0.064 (14)*
H5O	0.368 (6)	1.096 (5)	0.2184 (17)	0.057 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0218 (15)	0.0199 (14)	0.0252 (16)	−0.0016 (12)	0.0008 (12)	−0.0005 (13)
C2	0.0191 (13)	0.0192 (14)	0.0244 (16)	−0.0011 (12)	−0.0004 (12)	−0.0012 (13)
C3	0.0233 (14)	0.0205 (14)	0.0210 (15)	0.0005 (12)	0.0005 (12)	−0.0044 (12)
C4	0.0225 (14)	0.0241 (14)	0.0170 (14)	−0.0027 (13)	−0.0021 (12)	0.0009 (13)
C5	0.0221 (14)	0.0184 (13)	0.0226 (16)	0.0013 (12)	0.0002 (12)	0.0022 (13)
C6	0.0233 (14)	0.0202 (14)	0.0225 (15)	0.0006 (12)	0.0013 (12)	−0.0030 (13)
C7	0.0239 (15)	0.0243 (15)	0.0188 (15)	−0.0002 (13)	0.0003 (12)	0.0021 (12)
C8	0.0226 (14)	0.0222 (15)	0.0203 (15)	−0.0003 (12)	0.0028 (13)	−0.0006 (12)
C9	0.0375 (18)	0.0249 (15)	0.0182 (15)	0.0042 (14)	−0.0012 (13)	0.0018 (13)
C10	0.0383 (17)	0.0251 (15)	0.0177 (15)	0.0051 (14)	0.0001 (14)	0.0021 (13)
C11	0.0228 (14)	0.0227 (14)	0.0212 (16)	−0.0005 (13)	0.0015 (13)	0.0004 (13)
C12	0.0215 (14)	0.0240 (15)	0.0208 (15)	−0.0034 (12)	−0.0003 (12)	0.0021 (13)
C13	0.0368 (19)	0.0263 (15)	0.0205 (16)	−0.0014 (14)	−0.0022 (13)	0.0043 (14)
C14	0.0377 (18)	0.0235 (15)	0.0222 (17)	0.0008 (14)	−0.0020 (14)	0.0035 (13)
C15	0.0226 (14)	0.0233 (14)	0.0224 (16)	0.0000 (13)	−0.0003 (13)	0.0014 (13)
N1	0.0280 (14)	0.0219 (13)	0.0162 (13)	0.0026 (11)	0.0007 (11)	0.0003 (12)
N2	0.0274 (13)	0.0202 (12)	0.0190 (13)	0.0022 (11)	−0.0012 (11)	−0.0010 (11)
O1	0.0416 (13)	0.0300 (11)	0.0195 (11)	0.0041 (11)	−0.0022 (10)	0.0016 (10)
O2	0.0405 (13)	0.0239 (11)	0.0237 (12)	0.0090 (11)	−0.0026 (10)	−0.0022 (10)
O3	0.0419 (13)	0.0247 (11)	0.0167 (11)	0.0039 (10)	−0.0021 (10)	−0.0002 (9)
O4	0.0352 (12)	0.0231 (11)	0.0191 (12)	0.0077 (10)	0.0005 (10)	0.0010 (9)
O5	0.0401 (13)	0.0254 (11)	0.0195 (12)	0.0078 (10)	0.0018 (10)	−0.0029 (10)
O6	0.0410 (13)	0.0268 (11)	0.0219 (11)	0.0057 (10)	0.0037 (10)	−0.0040 (10)
O7	0.0377 (12)	0.0224 (10)	0.0227 (12)	0.0059 (10)	0.0018 (10)	−0.0005 (10)
O8	0.0347 (12)	0.0214 (10)	0.0208 (12)	0.0019 (10)	−0.0010 (10)	−0.0014 (9)
O9	0.0384 (13)	0.0217 (10)	0.0248 (12)	0.0042 (10)	0.0022 (10)	−0.0003 (10)

Geometric parameters (Å, º)

C1—O1	1.223 (4)	C10—H10A	0.9900
C1—O2	1.321 (4)	C10—H10B	0.9900
C1—C2	1.487 (4)	C11—O6	1.217 (4)
C2—C7	1.391 (4)	C11—N1	1.377 (4)
C2—C3	1.401 (4)	C12—O8	1.224 (3)
C3—C4	1.386 (4)	C12—N2	1.373 (4)
C3—H3	0.9500	C12—C13	1.501 (4)
C4—O3	1.369 (3)	C13—C14	1.531 (4)
C4—C5	1.387 (4)	C13—H13A	0.9900
C5—O4	1.361 (3)	C13—H13B	0.9900
C5—C6	1.408 (4)	C14—C15	1.508 (4)
C6—O5	1.364 (3)	C14—H14A	0.9900
C6—C7	1.378 (4)	C14—H14B	0.9900
C7—H7	0.9500	C15—O9	1.217 (4)
C8—O7	1.220 (3)	C15—N2	1.380 (4)
C8—N1	1.377 (4)	N1—H1N	0.87 (4)
C8—C9	1.498 (4)	N2—H2N	0.97 (5)
C9—C10	1.526 (4)	O2—H2O	0.92 (5)
C9—H9A	0.9900	O3—H3O	0.92 (4)
C9—H9B	0.9900	O4—H4O	0.95 (4)
C10—C11	1.502 (4)	O5—H5O	0.93 (4)
O1—C1—O2	122.9 (3)	C9—C10—H10B	110.8
O1—C1—C2	124.1 (3)	H10A—C10—H10B	108.8
O2—C1—C2	113.0 (3)	O6—C11—N1	123.9 (3)
C7—C2—C3	120.1 (3)	O6—C11—C10	128.1 (3)
C7—C2—C1	120.1 (3)	N1—C11—C10	108.1 (2)
C3—C2—C1	119.7 (3)	O8—C12—N2	123.5 (3)
C4—C3—C2	119.4 (3)	O8—C12—C13	127.5 (3)
C4—C3—H3	120.3	N2—C12—C13	109.0 (3)
C2—C3—H3	120.3	C12—C13—C14	104.6 (3)
O3—C4—C3	122.8 (3)	C12—C13—H13A	110.8
O3—C4—C5	116.7 (3)	C14—C13—H13A	110.8
C3—C4—C5	120.6 (3)	C12—C13—H13B	110.8
O4—C5—C4	117.5 (3)	C14—C13—H13B	110.8
O4—C5—C6	122.8 (3)	H13A—C13—H13B	108.9
C4—C5—C6	119.7 (3)	C15—C14—C13	104.8 (2)
O5—C6—C7	125.2 (3)	C15—C14—H14A	110.8
O5—C6—C5	115.0 (3)	C13—C14—H14A	110.8
C7—C6—C5	119.8 (3)	C15—C14—H14B	110.8
C6—C7—C2	120.3 (3)	C13—C14—H14B	110.8
C6—C7—H7	119.8	H14A—C14—H14B	108.9
C2—C7—H7	119.8	O9—C15—N2	123.1 (3)
O7—C8—N1	123.7 (3)	O9—C15—C14	128.5 (3)
O7—C8—C9	128.1 (3)	N2—C15—C14	108.4 (3)
N1—C8—C9	108.2 (2)	C8—N1—C11	113.6 (3)
C8—C9—C10	105.1 (2)	C8—N1—H1N	121 (3)
C8—C9—H9A	110.7	C11—N1—H1N	125 (3)
C10—C9—H9A	110.7	C12—N2—C15	113.1 (3)
C8—C9—H9B	110.7	C12—N2—H2N	124 (3)
C10—C9—H9B	110.7	C15—N2—H2N	123 (3)
H9A—C9—H9B	108.8	C1—O2—H2O	109 (3)
C11—C10—C9	105.0 (2)	C4—O3—H3O	105 (2)
C11—C10—H10A	110.8	C5—O4—H4O	115 (3)
C9—C10—H10A	110.8	C6—O5—H5O	110 (3)
C11—C10—H10B	110.8
O1—C1—C2—C7	−0.9 (4)	C1—C2—C7—C6	−177.8 (3)
O2—C1—C2—C7	178.5 (3)	O7—C8—C9—C10	177.6 (3)
O1—C1—C2—C3	−179.4 (3)	N1—C8—C9—C10	−1.9 (3)
O2—C1—C2—C3	0.1 (4)	C8—C9—C10—C11	3.4 (3)
C7—C2—C3—C4	−0.4 (4)	C9—C10—C11—O6	176.7 (3)
C1—C2—C3—C4	178.1 (3)	C9—C10—C11—N1	−3.7 (3)
C2—C3—C4—O3	−179.8 (3)	O8—C12—C13—C14	177.3 (3)
C2—C3—C4—C5	0.7 (4)	N2—C12—C13—C14	−3.2 (3)
O3—C4—C5—O4	−0.1 (4)	C12—C13—C14—C15	2.6 (3)
C3—C4—C5—O4	179.5 (3)	C13—C14—C15—O9	179.7 (3)
O3—C4—C5—C6	179.3 (3)	C13—C14—C15—N2	−1.3 (3)
C3—C4—C5—C6	−1.1 (4)	O7—C8—N1—C11	−180.0 (3)
O4—C5—C6—O5	1.3 (4)	C9—C8—N1—C11	−0.5 (3)
C4—C5—C6—O5	−178.1 (3)	O6—C11—N1—C8	−177.7 (3)
O4—C5—C6—C7	−179.3 (3)	C10—C11—N1—C8	2.7 (3)
C4—C5—C6—C7	1.3 (4)	O8—C12—N2—C15	−177.9 (3)
O5—C6—C7—C2	178.3 (3)	C13—C12—N2—C15	2.6 (3)
C5—C6—C7—C2	−1.1 (4)	O9—C15—N2—C12	178.3 (3)
C3—C2—C7—C6	0.6 (4)	C14—C15—N2—C12	−0.8 (3)

(SM-345THBAII)

Crystal data

C7H6O5·2(C4H5NO2)	Z = 2
Mr = 368.30	F(000) = 384
Triclinic, P1	Dx = 1.546 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.9225 (4) Å	Cell parameters from 3114 reflections
b = 11.7839 (10) Å	θ = 2.4–26.3°
c = 13.8540 (16) Å	µ = 0.13 mm^−1
α = 97.248 (8)°	T = 110 K
β = 96.773 (8)°	Needle, colourless
γ = 90.663 (6)°	0.22 × 0.20 × 0.18 mm
V = 791.35 (13) Å^3

Data collection

Xcalibur, Eos, Nova diffractometer	2784 independent reflections
Radiation source: Mova (Mo) X-ray Source	Rint = 0.070
Mirror monochromator	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET) (compiled Jul 11 2012,15:38:31) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −6→6
Tmin = 0.578, Tmax = 1.000	k = −14→14
11875 measured reflections	l = −17→17

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.100	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.237	w = 1/[σ^2(Fo^2) + (0.020P)^2 + 7.7428P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
3095 reflections	Δρmax = 0.45 e Å^−3
287 parameters	Δρmin = −0.43 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.7316 (11)	0.9583 (5)	0.0802 (4)	0.0179 (12)
C2	0.5366 (11)	0.9285 (5)	0.1466 (4)	0.0174 (12)
C3	0.4732 (12)	0.8153 (5)	0.1564 (4)	0.0187 (13)
C4	0.2850 (12)	0.7925 (5)	0.2193 (4)	0.0189 (13)
C5	0.1650 (12)	0.8832 (5)	0.2731 (4)	0.0205 (13)
C6	0.2288 (12)	0.9949 (5)	0.2630 (4)	0.0189 (13)
C7	0.4142 (12)	1.0193 (5)	0.1993 (4)	0.0170 (12)
C8	0.0109 (13)	0.4023 (6)	0.2508 (5)	0.0281 (15)
C9	−0.0264 (14)	0.3118 (6)	0.1641 (5)	0.0331 (16)
H9A	−0.0757	0.2372	0.1842	0.040*
H9B	0.1440	0.3034	0.1327	0.040*
C10	−0.2585 (16)	0.3516 (7)	0.0935 (6)	0.0345 (17)
C11	−0.3673 (14)	0.4558 (6)	0.1533 (5)	0.0291 (15)
C12	−0.4141 (12)	0.7142 (5)	0.4424 (4)	0.0198 (13)
C13	−0.5938 (14)	0.6479 (5)	0.4966 (5)	0.0245 (14)
C14	−0.7113 (14)	0.7380 (5)	0.5680 (5)	0.0229 (14)
C15	−0.6339 (12)	0.8503 (5)	0.5354 (4)	0.0195 (13)
N1	−0.2042 (12)	0.4772 (5)	0.2395 (4)	0.0299 (13)
N2	−0.4518 (10)	0.8286 (4)	0.4676 (4)	0.0211 (11)
H2N	−0.3681	0.8827	0.4429	0.025*
O1	0.7865 (8)	1.0580 (3)	0.0710 (3)	0.0190 (9)
O2	0.8417 (9)	0.8700 (3)	0.0314 (3)	0.0217 (10)
O3	0.2041 (9)	0.6856 (4)	0.2356 (3)	0.0244 (10)
O4	−0.0146 (8)	0.8636 (4)	0.3375 (3)	0.0210 (10)
O5	0.1138 (9)	1.0842 (4)	0.3155 (3)	0.0235 (10)
O6	0.1870 (10)	0.4114 (4)	0.3207 (4)	0.0374 (12)
O7	−0.5656 (9)	0.5104 (4)	0.1284 (3)	0.0290 (11)
O8	−0.7131 (8)	0.9439 (3)	0.5643 (3)	0.0222 (10)
O9	−0.2568 (9)	0.6749 (4)	0.3852 (3)	0.0257 (10)
H1N	−0.22 (2)	0.539 (9)	0.280 (8)	0.08 (4)*
H2O	0.961 (16)	0.901 (6)	−0.003 (6)	0.04 (2)*
H3	0.528 (13)	0.748 (5)	0.113 (5)	0.019 (16)*
H3O	0.296 (19)	0.645 (8)	0.209 (7)	0.06 (3)*
H4O	−0.048 (17)	0.794 (8)	0.343 (6)	0.05 (3)*
H5O	−0.034 (17)	1.055 (7)	0.340 (6)	0.04 (2)*
H7	0.461 (13)	1.096 (6)	0.195 (5)	0.019 (16)*
H10A	−0.195 (14)	0.376 (6)	0.037 (5)	0.030 (19)*
H10B	−0.403 (17)	0.294 (7)	0.083 (6)	0.05 (2)*
H13A	−0.732 (15)	0.610 (6)	0.448 (5)	0.031 (19)*
H13B	−0.492 (15)	0.597 (6)	0.523 (5)	0.03 (2)*
H14A	−0.623 (14)	0.745 (6)	0.635 (5)	0.028 (19)*
H14B	−0.918 (13)	0.728 (5)	0.564 (4)	0.018 (16)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.012 (3)	0.019 (3)	0.021 (3)	0.001 (2)	0.002 (2)	−0.002 (2)
C2	0.010 (3)	0.022 (3)	0.019 (3)	0.006 (2)	0.002 (2)	0.000 (2)
C3	0.018 (3)	0.019 (3)	0.019 (3)	0.003 (2)	0.005 (2)	−0.001 (2)
C4	0.016 (3)	0.019 (3)	0.022 (3)	0.004 (2)	0.004 (2)	0.002 (2)
C5	0.018 (3)	0.026 (3)	0.018 (3)	0.004 (2)	0.007 (2)	−0.001 (2)
C6	0.014 (3)	0.020 (3)	0.021 (3)	0.003 (2)	0.002 (2)	−0.004 (2)
C7	0.014 (3)	0.013 (3)	0.023 (3)	0.000 (2)	0.003 (2)	0.000 (2)
C8	0.025 (4)	0.026 (3)	0.035 (4)	0.001 (3)	0.009 (3)	0.007 (3)
C9	0.026 (4)	0.031 (4)	0.042 (4)	0.003 (3)	0.008 (3)	−0.004 (3)
C10	0.033 (4)	0.032 (4)	0.037 (4)	0.010 (3)	0.007 (3)	−0.002 (3)
C11	0.030 (4)	0.024 (3)	0.035 (4)	−0.003 (3)	0.013 (3)	0.006 (3)
C12	0.017 (3)	0.019 (3)	0.023 (3)	0.001 (2)	0.004 (2)	−0.003 (2)
C13	0.025 (4)	0.015 (3)	0.033 (4)	0.001 (3)	0.011 (3)	−0.002 (3)
C14	0.026 (4)	0.018 (3)	0.026 (4)	0.000 (3)	0.009 (3)	0.001 (3)
C15	0.018 (3)	0.019 (3)	0.022 (3)	0.002 (2)	0.004 (2)	0.000 (2)
N1	0.035 (3)	0.019 (3)	0.036 (3)	0.001 (2)	0.014 (3)	−0.003 (2)
N2	0.025 (3)	0.014 (3)	0.026 (3)	0.003 (2)	0.011 (2)	−0.001 (2)
O1	0.013 (2)	0.020 (2)	0.024 (2)	0.0015 (16)	0.0076 (17)	−0.0009 (17)
O2	0.021 (2)	0.017 (2)	0.028 (2)	0.0044 (17)	0.0108 (19)	−0.0001 (18)
O3	0.025 (2)	0.016 (2)	0.034 (3)	0.0067 (18)	0.016 (2)	−0.0001 (19)
O4	0.017 (2)	0.022 (2)	0.026 (2)	0.0068 (18)	0.0109 (18)	0.0004 (18)
O5	0.022 (2)	0.020 (2)	0.028 (3)	0.0064 (18)	0.0109 (19)	−0.0040 (18)
O6	0.035 (3)	0.037 (3)	0.039 (3)	−0.002 (2)	0.001 (2)	0.002 (2)
O7	0.029 (3)	0.021 (2)	0.038 (3)	0.006 (2)	0.009 (2)	0.003 (2)
O8	0.023 (2)	0.013 (2)	0.032 (3)	0.0056 (17)	0.0133 (19)	−0.0003 (17)
O9	0.025 (2)	0.021 (2)	0.031 (3)	0.0092 (18)	0.012 (2)	−0.0048 (18)

Geometric parameters (Å, º)

C1—O1	1.228 (7)	C10—H10A	0.95 (7)
C1—O2	1.324 (7)	C10—H10B	0.97 (8)
C1—C2	1.475 (8)	C11—O7	1.215 (8)
C2—C3	1.393 (8)	C11—N1	1.352 (9)
C2—C7	1.400 (8)	C12—O9	1.226 (7)
C3—C4	1.391 (8)	C12—N2	1.370 (7)
C3—H3	0.99 (6)	C12—C13	1.497 (9)
C4—O3	1.371 (7)	C13—C14	1.525 (8)
C4—C5	1.402 (8)	C13—H13A	0.96 (7)
C5—O4	1.366 (7)	C13—H13B	0.87 (7)
C5—C6	1.377 (9)	C14—C15	1.510 (8)
C6—O5	1.369 (7)	C14—H14A	0.97 (7)
C6—C7	1.394 (8)	C14—H14B	1.02 (6)
C7—H7	0.94 (7)	C15—O8	1.210 (7)
C8—O6	1.214 (8)	C15—N2	1.377 (8)
C8—N1	1.394 (9)	N1—H1N	0.87 (11)
C8—C9	1.495 (9)	N2—H2N	0.8800
C9—C10	1.532 (10)	O2—H2O	0.90 (8)
C9—H9A	0.9900	O3—H3O	0.75 (9)
C9—H9B	0.9900	O4—H4O	0.85 (9)
C10—C11	1.531 (9)	O5—H5O	0.92 (8)
O1—C1—O2	122.8 (5)	C9—C10—H10B	108 (5)
O1—C1—C2	122.0 (5)	H10A—C10—H10B	118 (6)
O2—C1—C2	115.2 (5)	O7—C11—N1	125.4 (6)
C3—C2—C7	121.0 (5)	O7—C11—C10	126.4 (7)
C3—C2—C1	121.9 (5)	N1—C11—C10	108.1 (6)
C7—C2—C1	117.1 (5)	O9—C12—N2	124.5 (6)
C4—C3—C2	119.3 (5)	O9—C12—C13	126.9 (5)
C4—C3—H3	115 (4)	N2—C12—C13	108.7 (5)
C2—C3—H3	124 (4)	C12—C13—C14	104.8 (5)
O3—C4—C3	125.3 (5)	C12—C13—H13A	107 (4)
O3—C4—C5	114.9 (5)	C14—C13—H13A	113 (4)
C3—C4—C5	119.8 (6)	C12—C13—H13B	107 (5)
O4—C5—C6	118.3 (5)	C14—C13—H13B	116 (5)
O4—C5—C4	121.1 (5)	H13A—C13—H13B	109 (6)
C6—C5—C4	120.5 (5)	C15—C14—C13	104.1 (5)
O5—C6—C5	121.0 (5)	C15—C14—H14A	103 (4)
O5—C6—C7	118.5 (5)	C13—C14—H14A	115 (4)
C5—C6—C7	120.4 (5)	C15—C14—H14B	111 (3)
C6—C7—C2	118.9 (5)	C13—C14—H14B	111 (3)
C6—C7—H7	120 (4)	H14A—C14—H14B	112 (5)
C2—C7—H7	121 (4)	O8—C15—N2	125.3 (6)
O6—C8—N1	124.2 (6)	O8—C15—C14	126.5 (5)
O6—C8—C9	128.7 (6)	N2—C15—C14	108.2 (5)
N1—C8—C9	107.1 (6)	C11—N1—C8	114.6 (6)
C8—C9—C10	105.9 (6)	C11—N1—H1N	121 (7)
C8—C9—H9A	110.6	C8—N1—H1N	124 (7)
C10—C9—H9A	110.6	C12—N2—C15	113.1 (5)
C8—C9—H9B	110.6	C12—N2—H2N	123.5
C10—C9—H9B	110.6	C15—N2—H2N	123.5
H9A—C9—H9B	108.7	C1—O2—H2O	105 (5)
C11—C10—C9	103.6 (6)	C4—O3—H3O	105 (7)
C11—C10—H10A	108 (4)	C5—O4—H4O	116 (6)
C9—C10—H10A	112 (4)	C6—O5—H5O	107 (5)
C11—C10—H10B	106 (5)
O1—C1—C2—C3	179.5 (6)	C1—C2—C7—C6	−179.9 (5)
O2—C1—C2—C3	−0.3 (8)	O6—C8—C9—C10	−173.0 (7)
O1—C1—C2—C7	0.1 (8)	N1—C8—C9—C10	8.6 (8)
O2—C1—C2—C7	−179.7 (5)	C8—C9—C10—C11	−8.2 (8)
C7—C2—C3—C4	0.2 (9)	C9—C10—C11—O7	−174.7 (7)
C1—C2—C3—C4	−179.2 (5)	C9—C10—C11—N1	5.2 (8)
C2—C3—C4—O3	179.9 (6)	O9—C12—C13—C14	171.7 (6)
C2—C3—C4—C5	−1.0 (9)	N2—C12—C13—C14	−7.9 (7)
O3—C4—C5—O4	1.1 (8)	C12—C13—C14—C15	10.8 (7)
C3—C4—C5—O4	−178.1 (6)	C13—C14—C15—O8	170.7 (6)
O3—C4—C5—C6	−179.8 (5)	C13—C14—C15—N2	−10.4 (7)
C3—C4—C5—C6	1.0 (9)	O7—C11—N1—C8	−179.9 (6)
O4—C5—C6—O5	−0.6 (9)	C10—C11—N1—C8	0.1 (8)
C4—C5—C6—O5	−179.7 (5)	O6—C8—N1—C11	175.8 (6)
O4—C5—C6—C7	179.0 (5)	C9—C8—N1—C11	−5.6 (8)
C4—C5—C6—C7	−0.1 (9)	O9—C12—N2—C15	−178.2 (6)
O5—C6—C7—C2	178.9 (5)	C13—C12—N2—C15	1.4 (7)
C5—C6—C7—C2	−0.7 (9)	O8—C15—N2—C12	−175.2 (6)
C3—C2—C7—C6	0.7 (9)	C14—C15—N2—C12	5.9 (7)

(SM-35DHBA)

Crystal data

3(C7H6O4)·C4H5NO2·3(H2O)	Z = 2
Mr = 615.49	F(000) = 644
Triclinic, P1	Dx = 1.535 Mg m^−3
a = 9.3161 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2092 (3) Å	Cell parameters from 9808 reflections
c = 13.7362 (7) Å	θ = 2.7–26.0°
α = 102.926 (3)°	µ = 0.13 mm^−1
β = 104.398 (4)°	T = 100 K
γ = 96.571 (3)°	Block, colorless
V = 1332.01 (11) Å^3	0.20 × 0.18 × 0.15 mm

Data collection

Xcalibur, Eos, Nova diffractometer	4753 reflections with I > 2σ(I)
Radiation source: Mova (Mo) X-ray Source	Rint = 0.030
Mirror monochromator	θmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET) (compiled Dec 3 2012,18:21:49) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −10→11
Tmin = 0.898, Tmax = 1.000	k = −8→13
9808 measured reflections	l = −16→14
5225 independent reflections

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.074	H-atom parameters constrained
wR(F^2) = 0.174	w = 1/[σ^2(Fo^2) + (0.0367P)^2 + 3.3023P] where P = (Fo^2 + 2Fc^2)/3
S = 1.21	(Δ/σ)max < 0.001
5225 reflections	Δρmax = 0.39 e Å^−3
388 parameters	Δρmin = −0.45 e Å^−3

Special details

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. There are two planar H-bond networks. The network containing O1/O2/O3/O4, O9/O10/O11/O12 and O2W is ordered. The network containing O5/O6/O7/O8 and O1W is apparently the same, but disordered over two inversion-related orientations in space group P-1. A l l H atoms in this plane (apart from H2W1, which points out of the plane) are refined with occupancy 0.5. The alternative H-bond sequences are: (1) ··· O7—H7A —> O1W-H1W2 —> O8—H8B —> O8 (2) ··· O7 <—- H1W3-O1W <—- H8A—O8 <— H8B—O8

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.0730 (3)	0.5967 (3)	0.4358 (2)	0.0124 (6)
C2	0.0226 (3)	0.4978 (2)	0.3361 (2)	0.0121 (6)
C3	−0.1309 (3)	0.4527 (3)	0.2915 (2)	0.0119 (6)
H3	−0.2019	0.4818	0.3259	0.014*
C4	−0.1786 (3)	0.3646 (3)	0.1961 (2)	0.0122 (6)
C5	−0.0749 (3)	0.3202 (3)	0.1464 (2)	0.0130 (6)
H5	−0.1083	0.2595	0.0812	0.016*
C6	0.0775 (3)	0.3652 (3)	0.1927 (2)	0.0116 (6)
C7	0.1280 (3)	0.4551 (3)	0.2883 (2)	0.0119 (6)
H7	0.2326	0.4863	0.3198	0.014*
C8	0.9347 (3)	0.8679 (3)	0.3753 (2)	0.0169 (6)
C9	0.8862 (3)	0.7717 (3)	0.2743 (2)	0.0168 (6)
C10	0.7336 (3)	0.7256 (3)	0.2297 (2)	0.0161 (6)
H10	0.6622	0.7523	0.2645	0.019*
C11	0.6874 (3)	0.6396 (3)	0.1330 (2)	0.0168 (6)
C12	0.7912 (3)	0.5985 (3)	0.0820 (2)	0.0174 (6)
H12	0.7585	0.5396	0.0158	0.021*
C13	0.9436 (3)	0.6452 (3)	0.1293 (2)	0.0149 (6)
C14	0.9929 (3)	0.7316 (3)	0.2254 (2)	0.0151 (6)
H14	1.0973	0.7630	0.2573	0.018*
C15	0.2003 (3)	0.8580 (3)	0.6852 (2)	0.0138 (6)
C16	0.2481 (3)	0.9530 (3)	0.7869 (2)	0.0131 (6)
C17	0.3999 (3)	1.0043 (3)	0.8306 (2)	0.0126 (6)
H17	0.4724	0.9791	0.7961	0.015*
C18	0.4436 (3)	1.0931 (2)	0.9259 (2)	0.0116 (6)
C19	0.3384 (3)	1.1306 (3)	0.9768 (2)	0.0138 (6)
H19	0.3697	1.1903	1.0425	0.017*
C20	0.1865 (3)	1.0797 (3)	0.9304 (2)	0.0115 (6)
C21	0.1405 (3)	0.9898 (3)	0.8357 (2)	0.0122 (6)
H21	0.0370	0.9541	0.8047	0.015*
C22	0.5419 (3)	0.7198 (3)	0.4556 (2)	0.0166 (6)
C23	0.6328 (4)	0.6825 (3)	0.5465 (2)	0.0215 (7)
H23A	0.7217	0.6507	0.5309	0.026*
H23B	0.5714	0.6172	0.5645	0.026*
C24	0.6812 (4)	0.8017 (3)	0.6352 (2)	0.0227 (7)
H24A	0.6465	0.7899	0.6955	0.027*
H24B	0.7922	0.8271	0.6581	0.027*
C25	0.6077 (3)	0.8971 (3)	0.5903 (2)	0.0170 (6)
N1	0.5296 (3)	0.8419 (2)	0.4875 (2)	0.0171 (5)
H1N	0.4771	0.8813	0.4466	0.021*
O1	−0.0248 (2)	0.64003 (19)	0.47538 (15)	0.0160 (4)
O2	0.2149 (2)	0.6330 (2)	0.47655 (16)	0.0212 (5)
H2O	0.2308	0.6888	0.5322	0.032*
O1W	0.3370 (3)	0.6994 (3)	0.17910 (19)	0.0380 (7)
H1W1	0.3817	0.6854	0.2363	0.057*
H1W2	0.2448	0.6693	0.1477	0.057*	0.5
H1W3	0.3992	0.6673	0.1501	0.057*	0.5
O3	−0.3288 (2)	0.3226 (2)	0.15043 (16)	0.0189 (5)
H3O	−0.3418	0.2700	0.0934	0.028*
O2W	0.4732 (3)	0.4073 (2)	0.25096 (18)	0.0266 (5)
H2W1	0.4775	0.4814	0.2854	0.040*
H2W2	0.5359	0.3811	0.2194	0.040*
O4	0.1787 (2)	0.3223 (2)	0.14297 (16)	0.0193 (5)
H4O	0.2665	0.3571	0.1792	0.029*
O3W	0.2182 (3)	0.9504 (2)	0.13650 (18)	0.0266 (5)
H3W1	0.1259	0.9288	0.1017	0.040*
H3W2	0.2641	0.9625	0.2006	0.040*
O5	0.8412 (3)	0.9056 (2)	0.42000 (18)	0.0238 (5)
O6	1.0782 (3)	0.9090 (2)	0.41235 (19)	0.0262 (5)
H6O	1.0956	0.9626	0.4694	0.039*
O7	0.5372 (2)	0.5958 (2)	0.08567 (19)	0.0256 (5)
H7A	0.4648	0.6242	0.1190	0.031*	0.5
H7B	0.5051	0.5369	0.0195	0.031*	0.5
O8	1.0460 (2)	0.6055 (2)	0.07869 (17)	0.0184 (5)
H8A	1.1505	0.6373	0.1096	0.022*	0.5
H8B	1.0125	0.5462	0.0128	0.022*	0.5
O9	0.2989 (2)	0.8157 (2)	0.64583 (16)	0.0209 (5)
O10	0.0584 (2)	0.8234 (2)	0.64233 (16)	0.0192 (5)
H10O	0.0433	0.7698	0.5855	0.029*
O11	0.5926 (2)	1.14531 (19)	0.97078 (16)	0.0158 (4)
H11O	0.6437	1.1148	0.9323	0.024*
O12	0.0806 (2)	1.11887 (19)	0.97762 (16)	0.0155 (4)
H12O	0.1234	1.1729	1.0339	0.023*
O13	0.4861 (2)	0.6548 (2)	0.36649 (16)	0.0199 (5)
O14	0.6153 (3)	1.0055 (2)	0.63426 (17)	0.0212 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0137 (14)	0.0116 (13)	0.0103 (13)	0.0014 (11)	0.0028 (11)	0.0008 (11)
C2	0.0177 (15)	0.0092 (13)	0.0089 (13)	0.0021 (11)	0.0039 (11)	0.0016 (10)
C3	0.0115 (14)	0.0119 (13)	0.0124 (13)	0.0031 (11)	0.0053 (11)	0.0006 (11)
C4	0.0088 (13)	0.0122 (13)	0.0138 (14)	0.0004 (10)	0.0014 (11)	0.0023 (11)
C5	0.0165 (15)	0.0101 (13)	0.0100 (13)	0.0014 (11)	0.0031 (11)	−0.0011 (10)
C6	0.0109 (14)	0.0124 (13)	0.0125 (13)	0.0029 (10)	0.0062 (11)	0.0019 (11)
C7	0.0089 (13)	0.0133 (13)	0.0120 (13)	0.0009 (10)	0.0018 (11)	0.0021 (11)
C8	0.0174 (15)	0.0166 (14)	0.0199 (15)	0.0045 (12)	0.0099 (12)	0.0057 (12)
C9	0.0184 (16)	0.0152 (14)	0.0221 (16)	0.0057 (12)	0.0103 (13)	0.0094 (12)
C10	0.0144 (15)	0.0151 (14)	0.0230 (16)	0.0037 (11)	0.0111 (12)	0.0064 (12)
C11	0.0132 (15)	0.0178 (15)	0.0227 (16)	0.0049 (12)	0.0073 (12)	0.0086 (12)
C12	0.0183 (16)	0.0178 (15)	0.0185 (15)	0.0054 (12)	0.0064 (12)	0.0068 (12)
C13	0.0149 (15)	0.0172 (14)	0.0185 (15)	0.0073 (11)	0.0099 (12)	0.0083 (12)
C14	0.0118 (14)	0.0159 (14)	0.0201 (15)	0.0038 (11)	0.0060 (12)	0.0071 (12)
C15	0.0152 (15)	0.0133 (14)	0.0110 (13)	0.0004 (11)	0.0028 (11)	0.0015 (11)
C16	0.0153 (15)	0.0106 (13)	0.0118 (14)	0.0017 (11)	0.0031 (11)	0.0009 (11)
C17	0.0126 (14)	0.0144 (14)	0.0108 (13)	0.0030 (11)	0.0055 (11)	0.0003 (11)
C18	0.0093 (13)	0.0095 (13)	0.0132 (14)	−0.0002 (10)	0.0006 (11)	0.0011 (11)
C19	0.0177 (15)	0.0118 (13)	0.0095 (13)	0.0011 (11)	0.0026 (11)	0.0002 (11)
C20	0.0111 (14)	0.0103 (13)	0.0146 (14)	0.0026 (10)	0.0050 (11)	0.0043 (11)
C21	0.0100 (14)	0.0117 (13)	0.0125 (13)	0.0006 (10)	0.0024 (11)	0.0001 (11)
C22	0.0142 (15)	0.0167 (14)	0.0214 (16)	0.0017 (11)	0.0107 (12)	0.0037 (12)
C23	0.0221 (17)	0.0196 (16)	0.0218 (16)	0.0070 (13)	0.0042 (13)	0.0038 (13)
C24	0.0226 (17)	0.0233 (16)	0.0172 (16)	0.0032 (13)	−0.0022 (13)	0.0045 (13)
C25	0.0141 (15)	0.0197 (16)	0.0177 (15)	0.0003 (12)	0.0075 (12)	0.0037 (12)
N1	0.0190 (13)	0.0163 (12)	0.0169 (13)	0.0045 (10)	0.0052 (10)	0.0054 (10)
O1	0.0158 (11)	0.0167 (10)	0.0123 (10)	0.0033 (8)	0.0040 (8)	−0.0028 (8)
O2	0.0146 (11)	0.0229 (12)	0.0130 (10)	−0.0058 (9)	−0.0006 (8)	−0.0117 (9)
O1W	0.0325 (15)	0.0540 (18)	0.0212 (13)	−0.0087 (13)	0.0005 (11)	0.0131 (12)
O3	0.0104 (10)	0.0218 (11)	0.0158 (11)	−0.0013 (8)	0.0022 (8)	−0.0088 (9)
O2W	0.0330 (14)	0.0185 (11)	0.0265 (13)	0.0030 (10)	0.0144 (11)	−0.0039 (9)
O4	0.0112 (11)	0.0228 (11)	0.0190 (11)	0.0018 (9)	0.0060 (9)	−0.0055 (9)
O3W	0.0301 (14)	0.0286 (13)	0.0164 (11)	−0.0005 (10)	0.0044 (10)	0.0020 (10)
O5	0.0203 (12)	0.0248 (12)	0.0254 (12)	0.0040 (9)	0.0118 (10)	−0.0011 (10)
O6	0.0189 (12)	0.0270 (12)	0.0274 (13)	−0.0008 (10)	0.0089 (10)	−0.0039 (10)
O7	0.0114 (11)	0.0308 (13)	0.0344 (14)	0.0044 (9)	0.0088 (10)	0.0053 (11)
O8	0.0123 (11)	0.0210 (11)	0.0210 (11)	0.0030 (9)	0.0080 (9)	0.0000 (9)
O9	0.0204 (12)	0.0203 (11)	0.0162 (11)	0.0017 (9)	0.0063 (9)	−0.0070 (9)
O10	0.0164 (11)	0.0201 (11)	0.0122 (10)	−0.0019 (9)	−0.0016 (8)	−0.0050 (8)
O11	0.0082 (10)	0.0200 (11)	0.0146 (10)	0.0004 (8)	0.0033 (8)	−0.0040 (8)
O12	0.0116 (10)	0.0171 (10)	0.0156 (10)	0.0011 (8)	0.0060 (8)	−0.0017 (8)
O13	0.0198 (12)	0.0195 (11)	0.0172 (11)	0.0016 (9)	0.0054 (9)	−0.0004 (9)
O14	0.0255 (12)	0.0158 (11)	0.0204 (11)	0.0017 (9)	0.0062 (9)	0.0022 (9)

Geometric parameters (Å, º)

C1—O1	1.262 (3)	C18—C19	1.389 (4)
C1—O2	1.278 (4)	C19—C20	1.392 (4)
C1—C2	1.486 (4)	C19—H19	0.9500
C2—C7	1.383 (4)	C20—O12	1.370 (3)
C2—C3	1.391 (4)	C20—C21	1.389 (4)
C3—C4	1.386 (4)	C21—H21	0.9500
C3—H3	0.9500	C22—O13	1.224 (4)
C4—O3	1.361 (3)	C22—N1	1.368 (4)
C4—C5	1.390 (4)	C22—C23	1.496 (4)
C5—C6	1.385 (4)	C23—C24	1.528 (4)
C5—H5	0.9500	C23—H23A	0.9900
C6—O4	1.365 (3)	C23—H23B	0.9900
C6—C7	1.398 (4)	C24—C25	1.498 (4)
C7—H7	0.9500	C24—H24A	0.9900
C8—O5	1.244 (4)	C24—H24B	0.9900
C8—O6	1.294 (4)	C25—O14	1.216 (4)
C8—C9	1.483 (4)	C25—N1	1.379 (4)
C9—C10	1.385 (4)	N1—H1N	0.8800
C9—C14	1.393 (4)	O2—H2O	0.8400
C10—C11	1.388 (4)	O1W—H1W1	0.8500
C10—H10	0.9500	O1W—H1W2	0.8500
C11—O7	1.367 (4)	O1W—H1W3	0.8500
C11—C12	1.390 (4)	O3—H3O	0.8400
C12—C13	1.390 (4)	O2W—H2W1	0.8500
C12—H12	0.9500	O2W—H2W2	0.8501
C13—O8	1.371 (3)	O4—H4O	0.8400
C13—C14	1.384 (4)	O3W—H3W1	0.8500
C14—H14	0.9500	O3W—H3W2	0.8500
C15—O9	1.263 (4)	O6—H6O	0.8400
C15—O10	1.280 (4)	O7—H7A	0.9500
C15—C16	1.483 (4)	O7—H7B	0.9500
C16—C21	1.389 (4)	O8—H8A	0.9500
C16—C17	1.389 (4)	O8—H8B	0.9500
C17—C18	1.389 (4)	O10—H10O	0.8400
C17—H17	0.9500	O11—H11O	0.8400
C18—O11	1.370 (3)	O12—H12O	0.8400
O1—C1—O2	123.7 (3)	O11—C18—C19	119.1 (2)
O1—C1—C2	119.0 (3)	O11—C18—C17	119.8 (3)
O2—C1—C2	117.3 (2)	C19—C18—C17	121.1 (3)
C7—C2—C3	121.5 (3)	C18—C19—C20	119.3 (3)
C7—C2—C1	119.6 (3)	C18—C19—H19	120.3
C3—C2—C1	118.9 (3)	C20—C19—H19	120.3
C4—C3—C2	118.9 (3)	O12—C20—C21	119.3 (3)
C4—C3—H3	120.5	O12—C20—C19	120.1 (2)
C2—C3—H3	120.5	C21—C20—C19	120.6 (3)
O3—C4—C3	119.3 (3)	C20—C21—C16	119.0 (3)
O3—C4—C5	120.0 (2)	C20—C21—H21	120.5
C3—C4—C5	120.7 (3)	C16—C21—H21	120.5
C6—C5—C4	119.5 (3)	O13—C22—N1	123.9 (3)
C6—C5—H5	120.3	O13—C22—C23	127.3 (3)
C4—C5—H5	120.3	N1—C22—C23	108.8 (3)
O4—C6—C5	119.3 (2)	C22—C23—C24	104.7 (2)
O4—C6—C7	119.9 (3)	C22—C23—H23A	110.8
C5—C6—C7	120.8 (3)	C24—C23—H23A	110.8
C2—C7—C6	118.5 (3)	C22—C23—H23B	110.8
C2—C7—H7	120.7	C24—C23—H23B	110.8
C6—C7—H7	120.7	H23A—C23—H23B	108.9
O5—C8—O6	123.2 (3)	C25—C24—C23	104.9 (3)
O5—C8—C9	121.0 (3)	C25—C24—H24A	110.8
O6—C8—C9	115.8 (3)	C23—C24—H24A	110.8
C10—C9—C14	121.5 (3)	C25—C24—H24B	110.8
C10—C9—C8	118.5 (3)	C23—C24—H24B	110.8
C14—C9—C8	120.0 (3)	H24A—C24—H24B	108.9
C9—C10—C11	118.6 (3)	O14—C25—N1	124.5 (3)
C9—C10—H10	120.7	O14—C25—C24	127.3 (3)
C11—C10—H10	120.7	N1—C25—C24	108.3 (3)
O7—C11—C10	119.8 (3)	C22—N1—C25	113.3 (3)
O7—C11—C12	119.1 (3)	C22—N1—H1N	123.4
C10—C11—C12	121.1 (3)	C25—N1—H1N	123.4
C13—C12—C11	118.9 (3)	C1—O2—H2O	109.5
C13—C12—H12	120.5	H1W1—O1W—H1W2	122.3
C11—C12—H12	120.5	H1W1—O1W—H1W3	90.8
O8—C13—C14	119.9 (3)	H1W2—O1W—H1W3	115.0
O8—C13—C12	118.9 (3)	C4—O3—H3O	109.5
C14—C13—C12	121.2 (3)	H2W1—O2W—H2W2	126.7
C13—C14—C9	118.6 (3)	C6—O4—H4O	109.5
C13—C14—H14	120.7	H3W1—O3W—H3W2	133.3
C9—C14—H14	120.7	C8—O6—H6O	109.5
O9—C15—O10	123.7 (3)	C11—O7—H7A	120.0
O9—C15—C16	119.5 (3)	C11—O7—H7B	120.0
O10—C15—C16	116.9 (3)	H7A—O7—H7B	120.0
C21—C16—C17	121.4 (3)	C13—O8—H8A	120.0
C21—C16—C15	119.6 (3)	C13—O8—H8B	120.0
C17—C16—C15	119.0 (3)	H8A—O8—H8B	120.0
C16—C17—C18	118.6 (3)	C15—O10—H10O	109.5
C16—C17—H17	120.7	C18—O11—H11O	109.5
C18—C17—H17	120.7	C20—O12—H12O	109.5
O1—C1—C2—C7	175.8 (3)	C12—C13—C14—C9	−0.1 (4)
O2—C1—C2—C7	−4.2 (4)	C10—C9—C14—C13	1.0 (4)
O1—C1—C2—C3	−2.4 (4)	C8—C9—C14—C13	−177.6 (3)
O2—C1—C2—C3	177.6 (3)	O9—C15—C16—C21	−173.1 (3)
C7—C2—C3—C4	−1.2 (4)	O10—C15—C16—C21	6.8 (4)
C1—C2—C3—C4	177.0 (2)	O9—C15—C16—C17	7.7 (4)
C2—C3—C4—O3	−178.2 (2)	O10—C15—C16—C17	−172.5 (3)
C2—C3—C4—C5	1.1 (4)	C21—C16—C17—C18	0.8 (4)
O3—C4—C5—C6	178.9 (3)	C15—C16—C17—C18	−180.0 (2)
C3—C4—C5—C6	−0.4 (4)	C16—C17—C18—O11	−179.9 (2)
C4—C5—C6—O4	−179.3 (2)	C16—C17—C18—C19	−0.1 (4)
C4—C5—C6—C7	−0.4 (4)	O11—C18—C19—C20	178.7 (2)
C3—C2—C7—C6	0.4 (4)	C17—C18—C19—C20	−1.1 (4)
C1—C2—C7—C6	−177.8 (2)	C18—C19—C20—O12	−177.6 (2)
O4—C6—C7—C2	179.2 (2)	C18—C19—C20—C21	1.8 (4)
C5—C6—C7—C2	0.4 (4)	O12—C20—C21—C16	178.3 (2)
O5—C8—C9—C10	0.9 (4)	C19—C20—C21—C16	−1.1 (4)
O6—C8—C9—C10	−178.9 (3)	C17—C16—C21—C20	−0.2 (4)
O5—C8—C9—C14	179.5 (3)	C15—C16—C21—C20	−179.4 (3)
O6—C8—C9—C14	−0.2 (4)	O13—C22—C23—C24	176.5 (3)
C14—C9—C10—C11	−1.4 (4)	N1—C22—C23—C24	−3.4 (3)
C8—C9—C10—C11	177.2 (3)	C22—C23—C24—C25	2.9 (3)
C9—C10—C11—O7	−177.8 (3)	C23—C24—C25—O14	179.6 (3)
C9—C10—C11—C12	1.0 (4)	C23—C24—C25—N1	−1.5 (3)
O7—C11—C12—C13	178.7 (3)	O13—C22—N1—C25	−177.3 (3)
C10—C11—C12—C13	−0.1 (4)	C23—C22—N1—C25	2.7 (3)
C11—C12—C13—O8	−179.5 (3)	O14—C25—N1—C22	178.2 (3)
C11—C12—C13—C14	−0.3 (4)	C24—C25—N1—C22	−0.7 (4)
O8—C13—C14—C9	179.0 (3)

(MM-4HBA)

Crystal data

C7H6O3·C4H3NO2	F(000) = 488
Mr = 235.19	Dx = 1.428 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1917 reflections
a = 10.8426 (8) Å	θ = 3.7–29.2°
b = 6.5202 (4) Å	µ = 0.12 mm^−1
c = 16.1326 (13) Å	T = 100 K
β = 106.391 (8)°	Block, colourless
V = 1094.16 (14) Å^3	0.25 × 0.22 × 0.20 mm
Z = 4

Data collection

Four-circle diffractometer	2375 independent reflections
Radiation source: Mova (Mo) X-ray Source	Rint = 0.026
Mirror monochromator	θmax = 30.1°, θmin = 2.6°
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −13→14
Tmin = 0.474, Tmax = 1.000	k = −8→8
5081 measured reflections	l = −22→21

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0479P)^2 + 0.089P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
2375 reflections	Δρmax = 0.15 e Å^−3
166 parameters	Δρmin = −0.17 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	−0.31889 (18)	0.4495 (3)	0.03777 (10)	0.0494 (4)
C2	−0.17956 (17)	0.4137 (2)	0.06675 (10)	0.0454 (4)
C3	−0.13011 (17)	0.2167 (3)	0.06916 (10)	0.0490 (4)
H3	−0.1871	0.1036	0.0530	0.059*
C4	0.00044 (17)	0.1836 (2)	0.09470 (11)	0.0483 (4)
H4	0.0335	0.0484	0.0956	0.058*
C5	0.08335 (16)	0.3480 (2)	0.11905 (10)	0.0460 (4)
C6	0.03574 (19)	0.5444 (2)	0.11860 (12)	0.0535 (5)
H6	0.0928	0.6568	0.1367	0.064*
C7	−0.09476 (18)	0.5762 (3)	0.09171 (11)	0.0520 (5)
H7	−0.1274	0.7117	0.0902	0.062*
C8	−0.10180 (18)	0.3047 (3)	0.29425 (12)	0.0592 (5)
H8	−0.1919	0.3277	0.2797	0.071*
C9	−0.0123 (2)	0.4464 (3)	0.31673 (12)	0.0595 (5)
H9	−0.0271	0.5890	0.3214	0.071*
C10	0.11522 (18)	0.3474 (2)	0.33368 (11)	0.0512 (5)
C11	−0.03821 (17)	0.1033 (3)	0.29552 (11)	0.0513 (4)
O1	−0.36003 (13)	0.63172 (19)	0.02864 (9)	0.0671 (4)
O2	−0.39267 (13)	0.2937 (2)	0.02309 (9)	0.0656 (4)
O3	0.21367 (11)	0.3237 (2)	0.14545 (9)	0.0611 (4)
O4	−0.08623 (14)	−0.06413 (19)	0.27932 (10)	0.0725 (4)
O5	0.22094 (13)	0.42560 (18)	0.35488 (9)	0.0695 (4)
N1	0.09208 (15)	0.1432 (2)	0.31986 (10)	0.0518 (4)
H1N	0.149 (2)	0.055 (3)	0.3259 (11)	0.060 (6)*
H2O	−0.4818 (11)	0.325 (4)	0.0054 (19)	0.152 (12)*
H3O	0.228 (3)	0.190 (5)	0.1421 (17)	0.124 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0419 (10)	0.0525 (10)	0.0522 (9)	0.0074 (8)	0.0105 (8)	0.0006 (8)
C2	0.0398 (9)	0.0476 (9)	0.0485 (8)	0.0050 (7)	0.0118 (7)	0.0021 (7)
C3	0.0401 (9)	0.0451 (9)	0.0580 (9)	0.0002 (7)	0.0077 (8)	−0.0014 (7)
C4	0.0432 (9)	0.0379 (8)	0.0613 (10)	0.0057 (7)	0.0105 (8)	0.0006 (7)
C5	0.0349 (8)	0.0440 (9)	0.0578 (9)	0.0022 (7)	0.0107 (8)	0.0051 (7)
C6	0.0452 (10)	0.0384 (9)	0.0746 (11)	−0.0019 (7)	0.0132 (9)	0.0010 (8)
C7	0.0467 (10)	0.0403 (9)	0.0685 (11)	0.0077 (8)	0.0156 (9)	0.0053 (8)
C8	0.0406 (10)	0.0546 (10)	0.0794 (12)	0.0069 (8)	0.0122 (9)	0.0142 (9)
C9	0.0558 (12)	0.0423 (9)	0.0776 (12)	0.0050 (9)	0.0145 (10)	0.0076 (9)
C10	0.0452 (10)	0.0410 (9)	0.0620 (10)	−0.0025 (8)	0.0065 (8)	0.0053 (7)
C11	0.0426 (10)	0.0446 (9)	0.0629 (10)	−0.0028 (8)	0.0089 (8)	0.0082 (8)
O1	0.0478 (7)	0.0605 (8)	0.0894 (9)	0.0152 (7)	0.0135 (7)	0.0003 (7)
O2	0.0383 (7)	0.0655 (9)	0.0877 (9)	0.0013 (6)	0.0095 (7)	−0.0045 (7)
O3	0.0346 (7)	0.0451 (7)	0.0983 (10)	0.0014 (5)	0.0102 (7)	−0.0009 (6)
O4	0.0541 (8)	0.0485 (7)	0.1072 (11)	−0.0121 (6)	0.0104 (8)	0.0047 (7)
O5	0.0480 (8)	0.0487 (7)	0.1006 (10)	−0.0114 (6)	0.0027 (7)	0.0000 (7)
N1	0.0375 (8)	0.0368 (7)	0.0745 (10)	0.0023 (6)	0.0049 (7)	0.0025 (7)

Geometric parameters (Å, º)

C1—O1	1.263 (2)	C6—C7	1.374 (3)
C1—O2	1.273 (2)	C8—C9	1.314 (3)
C1—C2	1.469 (2)	C8—C11	1.481 (2)
C2—C7	1.386 (2)	C9—C10	1.480 (3)
C2—C3	1.388 (2)	C10—O5	1.212 (2)
C3—C4	1.375 (2)	C10—N1	1.361 (2)
C4—C5	1.383 (2)	C11—O4	1.206 (2)
C5—O3	1.365 (2)	C11—N1	1.380 (2)
C5—C6	1.380 (2)
O1—C1—O2	123.11 (16)	C7—C6—C5	119.46 (16)
O1—C1—C2	118.97 (16)	C6—C7—C2	121.10 (15)
O2—C1—C2	117.92 (15)	C9—C8—C11	108.35 (17)
C7—C2—C3	118.67 (17)	C8—C9—C10	108.85 (16)
C7—C2—C1	120.63 (15)	O5—C10—N1	124.99 (17)
C3—C2—C1	120.70 (16)	O5—C10—C9	128.94 (17)
C4—C3—C2	120.71 (16)	N1—C10—C9	106.07 (15)
C3—C4—C5	119.66 (15)	O4—C11—N1	125.26 (17)
O3—C5—C6	117.51 (15)	O4—C11—C8	128.97 (17)
O3—C5—C4	122.10 (14)	N1—C11—C8	105.77 (14)
C6—C5—C4	120.38 (16)	C10—N1—C11	110.96 (15)
O1—C1—C2—C7	6.2 (3)	C3—C2—C7—C6	−0.2 (3)
O2—C1—C2—C7	−173.77 (16)	C1—C2—C7—C6	−179.75 (17)
O1—C1—C2—C3	−173.41 (16)	C11—C8—C9—C10	0.3 (2)
O2—C1—C2—C3	6.7 (3)	C8—C9—C10—O5	179.1 (2)
C7—C2—C3—C4	−0.8 (3)	C8—C9—C10—N1	−0.3 (2)
C1—C2—C3—C4	178.73 (16)	C9—C8—C11—O4	179.7 (2)
C2—C3—C4—C5	0.6 (3)	C9—C8—C11—N1	−0.2 (2)
C3—C4—C5—O3	179.59 (16)	O5—C10—N1—C11	−179.30 (19)
C3—C4—C5—C6	0.6 (3)	C9—C10—N1—C11	0.1 (2)
O3—C5—C6—C7	179.37 (17)	O4—C11—N1—C10	−179.87 (19)
C4—C5—C6—C7	−1.6 (3)	C8—C11—N1—C10	0.0 (2)
C5—C6—C7—C2	1.4 (3)

(MM-24DHBA)

Crystal data

C7H6O4·C4H3NO2	F(000) = 1040
Mr = 251.19	Dx = 1.540 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ya	Cell parameters from 9037 reflections
a = 12.5506 (4) Å	θ = 3.1–27.5°
b = 6.6807 (2) Å	µ = 0.13 mm^−1
c = 26.1586 (8) Å	T = 100 K
β = 98.815 (3)°	Plate, colourless
V = 2167.40 (12) Å^3	0.21 × 0.15 × 0.15 mm
Z = 8

Data collection

Four-circle diffractometer	2137 independent reflections
Radiation source: Mova (Mo) X-ray Source	Rint = 0.041
Mirror monochromator	θmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET) (compiled May 22 2014,16:03:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −15→15
Tmin = 0.847, Tmax = 1.000	k = −8→8
21462 measured reflections	l = −32→32

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.136	w = 1/[σ^2(Fo^2) + (0.0654P)^2 + 3.4709P] where P = (Fo^2 + 2Fc^2)/3
S = 1.16	(Δ/σ)max < 0.001
2137 reflections	Δρmax = 0.67 e Å^−3
179 parameters	Δρmin = −0.25 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
O1	0.95656 (13)	0.2237 (2)	0.18563 (6)	0.0241 (4)
O2	0.89695 (11)	0.3329 (2)	0.03973 (5)	0.0197 (3)
O3	0.78218 (11)	0.4179 (2)	−0.20469 (5)	0.0196 (3)
O4	0.78618 (11)	0.0854 (2)	−0.19456 (6)	0.0196 (3)
C5	0.82404 (15)	0.2857 (3)	−0.11981 (7)	0.0158 (4)
C6	0.83819 (15)	0.1151 (3)	−0.08799 (8)	0.0171 (4)
H6	0.8305	−0.0141	−0.1033	0.021*
O7	0.82433 (13)	0.6486 (2)	−0.12427 (6)	0.0246 (4)
O8	0.89140 (11)	−0.2721 (2)	0.06564 (5)	0.0207 (4)
C9	0.85977 (15)	0.4939 (3)	−0.04298 (7)	0.0175 (4)
H9	0.8670	0.6224	−0.0272	0.021*
C10	0.86304 (15)	0.1322 (3)	−0.03499 (8)	0.0185 (4)
H10	0.8730	0.0161	−0.0138	0.022*
C11	0.87332 (14)	0.3233 (3)	−0.01296 (7)	0.0166 (4)
C12	0.83552 (15)	0.4762 (3)	−0.09639 (7)	0.0163 (4)
N13	0.92014 (14)	0.0121 (3)	0.11522 (6)	0.0184 (4)
C14	0.79570 (15)	0.2679 (3)	−0.17607 (8)	0.0154 (4)
C15	0.95313 (16)	−0.1412 (3)	0.19493 (8)	0.0215 (5)
H15	0.9692	−0.1601	0.2313	0.026*
C16	0.94515 (15)	0.0567 (3)	0.16752 (7)	0.0187 (4)
C17	0.93405 (16)	−0.2843 (3)	0.16004 (8)	0.0200 (4)
H17	0.9341	−0.4238	0.1671	0.024*
C18	0.91247 (15)	−0.1912 (3)	0.10766 (8)	0.0178 (4)
H13	0.913 (2)	0.106 (5)	0.0907 (13)	0.046 (8)*
H4	0.766 (3)	0.080 (5)	−0.2251 (14)	0.052 (9)*
H2	0.895 (3)	0.463 (6)	0.0495 (14)	0.065 (11)*
H7	0.804 (3)	0.604 (6)	−0.1591 (16)	0.073 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0310 (8)	0.0224 (8)	0.0176 (8)	0.0000 (6)	−0.0004 (6)	−0.0042 (6)
O2	0.0265 (8)	0.0197 (8)	0.0118 (7)	−0.0006 (6)	−0.0003 (5)	−0.0003 (6)
O3	0.0266 (7)	0.0169 (7)	0.0142 (7)	−0.0012 (6)	−0.0003 (5)	0.0001 (6)
O4	0.0268 (8)	0.0173 (7)	0.0135 (7)	−0.0006 (6)	−0.0008 (6)	−0.0028 (6)
C5	0.0153 (9)	0.0200 (10)	0.0117 (9)	0.0000 (7)	0.0008 (7)	−0.0015 (8)
C6	0.0162 (9)	0.0171 (10)	0.0177 (9)	−0.0008 (8)	0.0017 (7)	−0.0019 (8)
O7	0.0395 (9)	0.0160 (8)	0.0174 (8)	−0.0005 (6)	0.0019 (6)	0.0006 (6)
O8	0.0241 (7)	0.0230 (8)	0.0141 (7)	−0.0014 (6)	0.0005 (6)	−0.0037 (6)
C9	0.0194 (9)	0.0163 (10)	0.0167 (10)	−0.0015 (8)	0.0025 (7)	−0.0057 (8)
C10	0.0186 (9)	0.0187 (10)	0.0180 (10)	0.0002 (8)	0.0024 (7)	0.0040 (8)
C11	0.0133 (9)	0.0217 (10)	0.0145 (9)	−0.0006 (8)	0.0014 (7)	−0.0004 (8)
C12	0.0155 (9)	0.0178 (10)	0.0156 (9)	−0.0006 (7)	0.0020 (7)	−0.0006 (8)
N13	0.0241 (9)	0.0177 (9)	0.0125 (8)	0.0010 (7)	−0.0003 (6)	0.0013 (7)
C14	0.0133 (9)	0.0182 (10)	0.0145 (10)	−0.0008 (7)	0.0019 (7)	−0.0020 (8)
C15	0.0238 (10)	0.0250 (11)	0.0150 (10)	0.0025 (8)	0.0011 (8)	0.0044 (8)
C16	0.0178 (9)	0.0228 (11)	0.0150 (9)	0.0013 (8)	0.0014 (7)	−0.0005 (8)
C17	0.0202 (10)	0.0203 (10)	0.0189 (10)	0.0004 (8)	0.0014 (8)	0.0026 (8)
C18	0.0153 (9)	0.0216 (10)	0.0167 (10)	0.0000 (8)	0.0027 (7)	−0.0013 (8)

Geometric parameters (Å, º)

O1—C16	1.212 (3)	O8—C18	1.217 (2)
O2—C11	1.366 (2)	C9—C11	1.380 (3)
O3—C14	1.247 (2)	C9—C12	1.389 (3)
O4—C14	1.311 (2)	C10—C11	1.399 (3)
C5—C6	1.406 (3)	N13—C18	1.374 (3)
C5—C12	1.411 (3)	N13—C16	1.388 (3)
C5—C14	1.465 (3)	C15—C17	1.318 (3)
C6—C10	1.378 (3)	C15—C16	1.500 (3)
O7—C12	1.359 (2)	C17—C18	1.491 (3)
C6—C5—C12	118.61 (17)	C18—N13—C16	110.74 (17)
C6—C5—C14	121.22 (18)	O3—C14—O4	122.00 (18)
C12—C5—C14	120.15 (17)	O3—C14—C5	121.86 (17)
C10—C6—C5	121.14 (18)	O4—C14—C5	116.13 (17)
C11—C9—C12	119.42 (18)	C17—C15—C16	108.45 (18)
C6—C10—C11	118.82 (18)	O1—C16—N13	125.31 (19)
O2—C11—C9	121.62 (18)	O1—C16—C15	128.99 (18)
O2—C11—C10	116.76 (17)	N13—C16—C15	105.70 (17)
C9—C11—C10	121.61 (17)	C15—C17—C18	108.79 (19)
O7—C12—C9	117.17 (17)	O8—C18—N13	124.74 (19)
O7—C12—C5	122.45 (17)	O8—C18—C17	128.9 (2)
C9—C12—C5	120.39 (18)	N13—C18—C17	106.32 (17)
C12—C5—C6—C10	−0.2 (3)	C6—C5—C14—O3	179.49 (17)
C14—C5—C6—C10	−178.87 (17)	C12—C5—C14—O3	0.8 (3)
C5—C6—C10—C11	0.5 (3)	C6—C5—C14—O4	−1.0 (3)
C12—C9—C11—O2	−179.82 (16)	C12—C5—C14—O4	−179.69 (16)
C12—C9—C11—C10	−0.1 (3)	C18—N13—C16—O1	−179.73 (19)
C6—C10—C11—O2	179.37 (16)	C18—N13—C16—C15	−0.3 (2)
C6—C10—C11—C9	−0.3 (3)	C17—C15—C16—O1	179.6 (2)
C11—C9—C12—O7	−179.18 (16)	C17—C15—C16—N13	0.1 (2)
C11—C9—C12—C5	0.5 (3)	C16—C15—C17—C18	0.0 (2)
C6—C5—C12—O7	179.30 (17)	C16—N13—C18—O8	179.97 (18)
C14—C5—C12—O7	−2.0 (3)	C16—N13—C18—C17	0.3 (2)
C6—C5—C12—C9	−0.3 (3)	C15—C17—C18—O8	−179.9 (2)
C14—C5—C12—C9	178.41 (17)	C15—C17—C18—N13	−0.2 (2)

(MM-35DHBA)

Crystal data

3(C7H6O4)·C4H3NO2·3(H2O)	V = 1331.4 (3) Å^3
Mr = 613.47	Z = 2
Triclinic, P1	F(000) = 628
a = 9.3796 (10) Å	Dx = 1.515 Mg m^−3
b = 10.3981 (12) Å	? radiation, λ = 0.71073 Å
c = 15.6415 (16) Å	µ = 0.13 mm^−1
α = 80.620 (9)°	T = 100 K
β = 72.913 (9)°	Block, colorless
γ = 66.089 (10)°	0.25 × 0.22 × 0.20 mm

Data collection

Xcalibur, Eos, Nova diffractometer	2571 reflections with I > 2σ(I)
Radiation source: Mova (Mo) X-ray Source	Rint = 0.124
Mirror monochromator	θmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET) (compiled Dec 3 2012,18:21:49) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −11→11
Tmin = 0.630, Tmax = 1.000	k = −11→12
16508 measured reflections	l = −18→18
4927 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.068	H-atom parameters constrained
wR(F^2) = 0.175	w = 1/[σ^2(Fo^2) + (0.081P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.91	(Δ/σ)max < 0.001
4927 reflections	Δρmax = 0.48 e Å^−3
388 parameters	Δρmin = −0.31 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1W	0.9935 (5)	1.1875 (4)	0.13626 (18)	0.0926 (14)
H1W1	1.0228	1.0988	0.1353	0.139*
H1W2	0.9299	1.1880	0.1070	0.139*	0.5
H1W3	1.0896	1.1768	0.1078	0.139*	0.5
O2W	1.3293 (4)	0.8100 (4)	0.22523 (18)	0.0843 (12)
H2W1	1.2911	0.8209	0.2812	0.127*
H2W2	1.4232	0.8060	0.1964	0.127*	0.5
H2W3	1.2586	0.8278	0.1966	0.127*	0.5
O3W	0.6698 (3)	0.4761 (3)	0.18455 (15)	0.0450 (7)
H3W1	0.6476	0.4744	0.2414	0.068*
H3W2	0.7596	0.4805	0.1546	0.068*	0.5
H3W3	0.6011	0.4926	0.1548	0.068*	0.5
C1	0.4126 (4)	1.1640 (3)	0.3284 (2)	0.0254 (8)
C2	0.4601 (4)	1.1640 (3)	0.2288 (2)	0.0248 (8)
C3	0.6044 (4)	1.1766 (3)	0.1828 (2)	0.0252 (8)
H3	0.6732	1.1838	0.2143	0.030*
C4	0.6478 (4)	1.1787 (3)	0.0900 (2)	0.0270 (8)
C5	0.5463 (4)	1.1688 (4)	0.0438 (2)	0.0325 (9)
H5	0.5766	1.1692	−0.0197	0.039*
C6	0.4010 (4)	1.1585 (4)	0.0913 (2)	0.0309 (9)
C7	0.3569 (4)	1.1539 (3)	0.1847 (2)	0.0270 (8)
H7	0.2587	1.1440	0.2172	0.032*
C8	0.7190 (4)	0.8389 (3)	0.4167 (2)	0.0255 (8)
C9	0.7694 (4)	0.8370 (3)	0.3173 (2)	0.0231 (8)
C10	0.9111 (4)	0.8550 (3)	0.2722 (2)	0.0257 (8)
H10	0.9755	0.8689	0.3039	0.031*
C11	0.9575 (4)	0.8524 (3)	0.1792 (2)	0.0222 (8)
C12	0.8633 (4)	0.8346 (3)	0.1326 (2)	0.0249 (8)
H12	0.8957	0.8343	0.0690	0.030*
C13	0.7208 (4)	0.8169 (3)	0.1790 (2)	0.0218 (7)
C14	0.6728 (4)	0.8177 (3)	0.2726 (2)	0.0266 (8)
H14	0.5758	0.8053	0.3049	0.032*
C15	1.0657 (4)	0.4973 (3)	0.3729 (2)	0.0242 (8)
C16	1.1172 (4)	0.4994 (3)	0.2728 (2)	0.0229 (8)
C17	1.2626 (4)	0.5117 (3)	0.2276 (2)	0.0227 (8)
H17	1.3317	0.5169	0.2596	0.027*
C18	1.3053 (4)	0.5163 (3)	0.1346 (2)	0.0219 (7)
C19	1.2043 (4)	0.5087 (3)	0.0883 (2)	0.0239 (8)
H19	1.2339	0.5127	0.0247	0.029*
C20	1.0603 (4)	0.4955 (3)	0.1345 (2)	0.0229 (8)
C21	1.0154 (4)	0.4904 (3)	0.2279 (2)	0.0235 (8)
H21	0.9167	0.4809	0.2599	0.028*
C22	0.6843 (4)	1.3640 (4)	0.4081 (2)	0.0277 (8)
C23	0.8247 (4)	1.2460 (4)	0.3639 (2)	0.0318 (9)
H23	0.8659	1.2377	0.3010	0.038*
C24	0.8853 (4)	1.1524 (4)	0.4255 (2)	0.0313 (9)
H24	0.9764	1.0665	0.4147	0.038*
C25	0.7838 (4)	1.2075 (4)	0.5151 (2)	0.0278 (8)
O1	0.5047 (3)	1.1735 (2)	0.36978 (15)	0.0318 (6)
O2	0.2768 (3)	1.1523 (2)	0.36718 (15)	0.0366 (6)
H2O	0.2605	1.1524	0.4229	0.055*
O3	0.7915 (3)	1.1878 (2)	0.04298 (15)	0.0391 (7)
H3A	0.8623	1.1929	0.0739	0.059*	0.5
H3B	0.8207	1.1892	−0.0206	0.059*	0.5
O4	0.2998 (3)	1.1511 (3)	0.04617 (16)	0.0475 (7)
H4A	0.3294	1.1530	−0.0174	0.071*	0.5
H4B	0.2000	1.1440	0.0784	0.071*	0.5
O5	0.8095 (3)	0.8498 (2)	0.45832 (15)	0.0343 (6)
O6	0.5829 (3)	0.8282 (2)	0.45564 (15)	0.0351 (6)
H6O	0.5655	0.8307	0.5113	0.053*
O7	1.0997 (3)	0.8682 (2)	0.13292 (15)	0.0327 (6)
H7A	1.1320	0.8667	0.0694	0.049*	0.5
H7B	1.1652	0.8806	0.1645	0.049*	0.5
O8	0.6273 (3)	0.7986 (2)	0.13341 (15)	0.0332 (6)
H8A	0.6595	0.7979	0.0699	0.050*	0.5
H8B	0.5299	0.7865	0.1652	0.050*	0.5
O9	1.1705 (3)	0.5027 (2)	0.41084 (14)	0.0325 (6)
H9O	1.1343	0.5006	0.4667	0.049*
O10	0.9341 (3)	0.4922 (2)	0.41518 (14)	0.0301 (6)
O11	1.4474 (3)	0.5297 (2)	0.08855 (14)	0.0303 (6)
H11A	1.4765	0.5338	0.0249	0.045*	0.5
H11B	1.5172	0.5349	0.1202	0.045*	0.5
O12	0.9588 (3)	0.4906 (2)	0.08873 (14)	0.0307 (6)
H12A	0.9872	0.4963	0.0251	0.046*	0.5
H12B	0.8598	0.4815	0.1206	0.046*	0.5
O13	0.5955 (3)	1.4703 (2)	0.37494 (15)	0.0338 (6)
O14	0.7984 (3)	1.1530 (2)	0.58906 (16)	0.0369 (6)
N1	0.6660 (3)	1.3355 (3)	0.49952 (17)	0.0285 (7)
H1N	0.5909	1.3905	0.5413	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1W	0.158 (3)	0.138 (3)	0.0313 (18)	−0.132 (3)	0.028 (2)	−0.0302 (19)
O2W	0.134 (3)	0.139 (3)	0.0228 (16)	−0.112 (3)	0.0100 (18)	−0.0148 (18)
O3W	0.0689 (19)	0.0647 (19)	0.0166 (13)	−0.0448 (16)	−0.0094 (13)	0.0070 (13)
C1	0.0258 (19)	0.030 (2)	0.0196 (19)	−0.0139 (16)	−0.0008 (16)	0.0005 (15)
C2	0.031 (2)	0.0224 (19)	0.0153 (18)	−0.0095 (16)	0.0001 (15)	0.0007 (15)
C3	0.030 (2)	0.028 (2)	0.0177 (19)	−0.0100 (16)	−0.0060 (16)	−0.0016 (15)
C4	0.0233 (19)	0.031 (2)	0.022 (2)	−0.0112 (16)	0.0016 (16)	0.0002 (16)
C5	0.027 (2)	0.049 (2)	0.0123 (18)	−0.0089 (18)	0.0000 (16)	−0.0013 (17)
C6	0.029 (2)	0.044 (2)	0.0169 (19)	−0.0122 (18)	−0.0052 (16)	−0.0008 (17)
C7	0.0233 (18)	0.036 (2)	0.020 (2)	−0.0103 (16)	−0.0033 (15)	−0.0016 (16)
C8	0.0236 (19)	0.031 (2)	0.0188 (18)	−0.0132 (16)	0.0008 (15)	0.0024 (15)
C9	0.0269 (19)	0.0248 (19)	0.0154 (18)	−0.0108 (16)	0.0004 (15)	−0.0028 (15)
C10	0.030 (2)	0.027 (2)	0.0200 (19)	−0.0110 (16)	−0.0047 (16)	−0.0023 (15)
C11	0.0220 (18)	0.0219 (19)	0.0216 (19)	−0.0111 (15)	0.0001 (15)	−0.0008 (15)
C12	0.0311 (19)	0.0236 (19)	0.0165 (18)	−0.0100 (16)	−0.0017 (15)	−0.0004 (15)
C13	0.0245 (18)	0.0223 (19)	0.0182 (18)	−0.0081 (15)	−0.0069 (15)	0.0002 (15)
C14	0.0276 (19)	0.031 (2)	0.0188 (19)	−0.0151 (16)	0.0024 (15)	0.0008 (16)
C15	0.0279 (19)	0.029 (2)	0.0156 (18)	−0.0126 (16)	−0.0021 (16)	−0.0020 (15)
C16	0.0285 (19)	0.0233 (19)	0.0150 (18)	−0.0099 (16)	−0.0037 (16)	0.0010 (15)
C17	0.0268 (19)	0.0251 (19)	0.0175 (19)	−0.0118 (16)	−0.0060 (15)	0.0011 (15)
C18	0.0241 (18)	0.0243 (19)	0.0158 (18)	−0.0118 (15)	0.0008 (15)	−0.0008 (15)
C19	0.031 (2)	0.0253 (19)	0.0146 (17)	−0.0119 (16)	−0.0013 (15)	−0.0024 (15)
C20	0.0239 (18)	0.028 (2)	0.0186 (19)	−0.0127 (15)	−0.0043 (15)	−0.0015 (15)
C21	0.0264 (18)	0.0248 (19)	0.0163 (18)	−0.0107 (15)	0.0004 (15)	−0.0016 (15)
C22	0.0305 (19)	0.032 (2)	0.0203 (19)	−0.0147 (17)	−0.0035 (16)	0.0002 (17)
C23	0.041 (2)	0.035 (2)	0.0171 (19)	−0.0162 (19)	−0.0022 (17)	−0.0011 (17)
C24	0.033 (2)	0.031 (2)	0.028 (2)	−0.0110 (17)	−0.0041 (17)	−0.0044 (17)
C25	0.032 (2)	0.032 (2)	0.020 (2)	−0.0158 (17)	−0.0038 (16)	0.0005 (17)
O1	0.0366 (14)	0.0451 (16)	0.0203 (13)	−0.0220 (12)	−0.0074 (11)	−0.0012 (11)
O2	0.0409 (15)	0.0553 (17)	0.0155 (13)	−0.0240 (13)	−0.0039 (12)	0.0026 (12)
O3	0.0330 (15)	0.0584 (17)	0.0183 (13)	−0.0204 (13)	0.0054 (11)	0.0044 (12)
O4	0.0367 (15)	0.083 (2)	0.0230 (14)	−0.0169 (15)	−0.0097 (12)	−0.0150 (14)
O5	0.0381 (15)	0.0568 (17)	0.0188 (13)	−0.0292 (13)	−0.0072 (12)	−0.0007 (12)
O6	0.0372 (15)	0.0561 (17)	0.0144 (13)	−0.0244 (13)	0.0002 (11)	−0.0022 (12)
O7	0.0319 (14)	0.0446 (16)	0.0225 (13)	−0.0233 (12)	0.0058 (11)	−0.0040 (12)
O8	0.0342 (14)	0.0521 (16)	0.0195 (13)	−0.0199 (12)	−0.0100 (11)	−0.0036 (12)
O9	0.0344 (14)	0.0550 (17)	0.0118 (12)	−0.0228 (12)	−0.0027 (11)	−0.0025 (11)
O10	0.0335 (14)	0.0445 (16)	0.0155 (13)	−0.0217 (12)	−0.0009 (11)	−0.0010 (11)
O11	0.0287 (13)	0.0500 (16)	0.0163 (12)	−0.0231 (12)	−0.0008 (11)	−0.0001 (11)
O12	0.0323 (13)	0.0506 (16)	0.0137 (12)	−0.0214 (12)	−0.0051 (10)	0.0002 (11)
O13	0.0386 (15)	0.0349 (15)	0.0211 (13)	−0.0097 (12)	−0.0053 (12)	0.0018 (12)
O14	0.0417 (15)	0.0416 (16)	0.0212 (14)	−0.0117 (12)	−0.0067 (11)	0.0023 (12)
N1	0.0309 (16)	0.0316 (18)	0.0146 (16)	−0.0078 (14)	0.0007 (13)	−0.0015 (13)

Geometric parameters (Å, º)

O1W—H1W1	0.8499	C15—O9	1.312 (4)
O1W—H1W2	0.8499	C15—C16	1.495 (4)
O1W—H1W3	0.8499	C16—C21	1.379 (4)
O2W—H2W1	0.8500	C16—C17	1.386 (4)
O2W—H2W2	0.8501	C17—C18	1.389 (4)
O2W—H2W3	0.8501	C17—H17	0.9500
O3W—H3W1	0.8499	C18—O11	1.367 (4)
O3W—H3W2	0.8500	C18—C19	1.382 (4)
O3W—H3W3	0.8501	C19—C20	1.382 (4)
C1—O1	1.262 (4)	C19—H19	0.9500
C1—O2	1.286 (4)	C20—O12	1.369 (3)
C1—C2	1.489 (5)	C20—C21	1.395 (4)
C2—C3	1.382 (4)	C21—H21	0.9500
C2—C7	1.387 (4)	C22—O13	1.227 (4)
C3—C4	1.387 (5)	C22—N1	1.386 (4)
C3—H3	0.9500	C22—C23	1.466 (5)
C4—O3	1.367 (4)	C23—C24	1.330 (4)
C4—C5	1.394 (4)	C23—H23	0.9500
C5—C6	1.385 (5)	C24—C25	1.494 (5)
C5—H5	0.9500	C24—H24	0.9500
C6—O4	1.370 (4)	C25—O14	1.223 (4)
C6—C7	1.394 (5)	C25—N1	1.383 (4)
C7—H7	0.9500	O2—H2O	0.8400
C8—O5	1.258 (4)	O3—H3A	0.9500
C8—O6	1.285 (4)	O3—H3B	0.9500
C8—C9	1.488 (4)	O4—H4A	0.9500
C9—C10	1.381 (4)	O4—H4B	0.9500
C9—C14	1.383 (4)	O6—H6O	0.8400
C10—C11	1.391 (5)	O7—H7A	0.9500
C10—H10	0.9500	O7—H7B	0.9500
C11—O7	1.379 (4)	O8—H8A	0.9500
C11—C12	1.380 (4)	O8—H8B	0.9500
C12—C13	1.390 (4)	O9—H9O	0.8400
C12—H12	0.9500	O11—H11A	0.9500
C13—O8	1.365 (3)	O11—H11B	0.9500
C13—C14	1.401 (4)	O12—H12A	0.9500
C14—H14	0.9500	O12—H12B	0.9500
C15—O10	1.235 (4)	N1—H1N	0.8800
H1W1—O1W—H1W2	82.4	C21—C16—C17	121.7 (3)
H1W1—O1W—H1W3	87.2	C21—C16—C15	118.0 (3)
H1W2—O1W—H1W3	118.1	C17—C16—C15	120.2 (3)
H2W1—O2W—H2W2	124.4	C16—C17—C18	118.8 (3)
H2W1—O2W—H2W3	114.2	C16—C17—H17	120.6
H2W2—O2W—H2W3	119.1	C18—C17—H17	120.6
H3W1—O3W—H3W2	118.6	O11—C18—C19	119.7 (3)
H3W1—O3W—H3W3	124.2	O11—C18—C17	119.8 (3)
H3W2—O3W—H3W3	115.7	C19—C18—C17	120.4 (3)
O1—C1—O2	123.8 (3)	C20—C19—C18	120.0 (3)
O1—C1—C2	120.1 (3)	C20—C19—H19	120.0
O2—C1—C2	116.1 (3)	C18—C19—H19	120.0
C3—C2—C7	121.8 (3)	O12—C20—C19	120.1 (3)
C3—C2—C1	119.1 (3)	O12—C20—C21	119.4 (3)
C7—C2—C1	119.1 (3)	C19—C20—C21	120.5 (3)
C2—C3—C4	119.2 (3)	C16—C21—C20	118.6 (3)
C2—C3—H3	120.4	C16—C21—H21	120.7
C4—C3—H3	120.4	C20—C21—H21	120.7
O3—C4—C3	120.3 (3)	O13—C22—N1	123.7 (3)
O3—C4—C5	119.4 (3)	O13—C22—C23	129.4 (3)
C3—C4—C5	120.3 (3)	N1—C22—C23	106.9 (3)
C6—C5—C4	119.5 (3)	C24—C23—C22	109.4 (3)
C6—C5—H5	120.2	C24—C23—H23	125.3
C4—C5—H5	120.2	C22—C23—H23	125.3
O4—C6—C5	119.7 (3)	C23—C24—C25	107.3 (3)
O4—C6—C7	119.4 (3)	C23—C24—H24	126.3
C5—C6—C7	120.9 (3)	C25—C24—H24	126.3
C2—C7—C6	118.3 (3)	O14—C25—N1	125.0 (3)
C2—C7—H7	120.8	O14—C25—C24	128.1 (3)
C6—C7—H7	120.8	N1—C25—C24	106.8 (3)
O5—C8—O6	123.4 (3)	C1—O2—H2O	109.5
O5—C8—C9	119.7 (3)	C4—O3—H3A	120.0
O6—C8—C9	116.9 (3)	C4—O3—H3B	120.0
C10—C9—C14	121.9 (3)	H3A—O3—H3B	120.0
C10—C9—C8	119.0 (3)	C6—O4—H4A	120.0
C14—C9—C8	119.1 (3)	C6—O4—H4B	120.0
C9—C10—C11	118.5 (3)	H4A—O4—H4B	120.0
C9—C10—H10	120.7	C8—O6—H6O	109.5
C11—C10—H10	120.7	C11—O7—H7A	120.0
O7—C11—C12	119.4 (3)	C11—O7—H7B	120.0
O7—C11—C10	119.5 (3)	H7A—O7—H7B	120.0
C12—C11—C10	121.1 (3)	C13—O8—H8A	120.0
C11—C12—C13	119.7 (3)	C13—O8—H8B	120.0
C11—C12—H12	120.2	H8A—O8—H8B	120.0
C13—C12—H12	120.2	C15—O9—H9O	109.5
O8—C13—C12	120.1 (3)	C18—O11—H11A	120.0
O8—C13—C14	119.8 (3)	C18—O11—H11B	120.0
C12—C13—C14	120.2 (3)	H11A—O11—H11B	120.0
C9—C14—C13	118.6 (3)	C20—O12—H12A	120.0
C9—C14—H14	120.7	C20—O12—H12B	120.0
C13—C14—H14	120.7	H12A—O12—H12B	120.0
O10—C15—O9	123.5 (3)	C25—N1—C22	109.6 (3)
O10—C15—C16	122.0 (3)	C25—N1—H1N	125.2
O9—C15—C16	114.5 (3)	C22—N1—H1N	125.2
O1—C1—C2—C3	−0.9 (5)	C8—C9—C14—C13	179.6 (3)
O2—C1—C2—C3	179.8 (3)	O8—C13—C14—C9	−179.8 (3)
O1—C1—C2—C7	−179.8 (3)	C12—C13—C14—C9	0.3 (5)
O2—C1—C2—C7	1.0 (5)	O10—C15—C16—C21	−2.3 (5)
C7—C2—C3—C4	−0.3 (5)	O9—C15—C16—C21	178.4 (3)
C1—C2—C3—C4	−179.1 (3)	O10—C15—C16—C17	177.0 (3)
C2—C3—C4—O3	−178.5 (3)	O9—C15—C16—C17	−2.3 (4)
C2—C3—C4—C5	0.3 (5)	C21—C16—C17—C18	0.6 (5)
O3—C4—C5—C6	179.6 (3)	C15—C16—C17—C18	−178.7 (3)
C3—C4—C5—C6	0.7 (5)	C16—C17—C18—O11	179.4 (3)
C4—C5—C6—O4	179.0 (3)	C16—C17—C18—C19	0.0 (5)
C4—C5—C6—C7	−1.8 (5)	O11—C18—C19—C20	−179.8 (3)
C3—C2—C7—C6	−0.8 (5)	C17—C18—C19—C20	−0.5 (5)
C1—C2—C7—C6	178.0 (3)	C18—C19—C20—O12	178.8 (3)
O4—C6—C7—C2	−178.9 (3)	C18—C19—C20—C21	0.3 (5)
C5—C6—C7—C2	1.9 (5)	C17—C16—C21—C20	−0.7 (5)
O5—C8—C9—C10	−3.5 (5)	C15—C16—C21—C20	178.6 (3)
O6—C8—C9—C10	176.9 (3)	O12—C20—C21—C16	−178.2 (3)
O5—C8—C9—C14	176.7 (3)	C19—C20—C21—C16	0.3 (5)
O6—C8—C9—C14	−2.8 (5)	O13—C22—C23—C24	−179.8 (3)
C14—C9—C10—C11	−0.5 (5)	N1—C22—C23—C24	0.5 (4)
C8—C9—C10—C11	179.7 (3)	C22—C23—C24—C25	0.0 (4)
C9—C10—C11—O7	−179.1 (3)	C23—C24—C25—O14	179.6 (3)
C9—C10—C11—C12	1.0 (5)	C23—C24—C25—N1	−0.4 (4)
O7—C11—C12—C13	179.2 (3)	O14—C25—N1—C22	−179.3 (3)
C10—C11—C12—C13	−0.9 (5)	C24—C25—N1—C22	0.7 (3)
C11—C12—C13—O8	−179.7 (3)	O13—C22—N1—C25	179.5 (3)
C11—C12—C13—C14	0.2 (5)	C23—C22—N1—C25	−0.7 (3)
C10—C9—C14—C13	−0.1 (5)

(GM-4HBA)

Crystal data

2(C7H6O3)·C5H7NO2	F(000) = 1632
Mr = 389.35	Dx = 1.425 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 4448 reflections
a = 40.692 (3) Å	θ = 3.2–27.3°
b = 5.4524 (3) Å	µ = 0.11 mm^−1
c = 16.3546 (9) Å	T = 100 K
V = 3628.6 (4) Å^3	Block, colourless
Z = 8	0.25 × 0.20 × 0.18 mm

Data collection

Four-circle diffractometer	4868 reflections with I > 2σ(I)
Radiation source: Mova (Mo) X-ray Source	Rint = 0.059
Mirror monochromator	θmax = 26.0°, θmin = 2.5°
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −40→50
Tmin = 0.664, Tmax = 1.000	k = −6→6
15134 measured reflections	l = −15→20
5638 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.048	w = 1/[σ^2(Fo^2) + (0.0464P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.108	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.22 e Å^−3
5638 reflections	Δρmin = −0.22 e Å^−3
594 parameters	Absolute structure: Refined as an inversion twin.
1 restraint

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.06639 (10)	0.7908 (7)	0.3476 (2)	0.0187 (9)
C2	0.03065 (9)	0.7757 (6)	0.3617 (2)	0.0179 (8)
C3	0.01174 (10)	0.5871 (7)	0.3279 (3)	0.0212 (9)
H3	0.0219	0.4652	0.2950	0.025*
C4	−0.02167 (9)	0.5777 (6)	0.3421 (3)	0.0209 (9)
H4	−0.0345	0.4492	0.3192	0.025*
C5	−0.03650 (9)	0.7565 (7)	0.3899 (2)	0.0205 (9)
C6	−0.01791 (10)	0.9458 (7)	0.4232 (3)	0.0247 (10)
H6	−0.0282	1.0685	0.4556	0.030*
C7	0.01549 (10)	0.9552 (7)	0.4092 (3)	0.0231 (9)
H7	0.0282	1.0844	0.4321	0.028*
C8	0.16007 (10)	0.7687 (7)	0.3398 (3)	0.0193 (9)
C9	0.19567 (9)	0.7337 (6)	0.3510 (2)	0.0173 (8)
C10	0.21504 (10)	0.9019 (7)	0.3930 (3)	0.0210 (9)
H10	0.2052	1.0421	0.4172	0.025*
C11	0.24872 (10)	0.8666 (7)	0.3998 (3)	0.0237 (9)
H11	0.2618	0.9815	0.4289	0.028*
C12	0.26313 (9)	0.6624 (7)	0.3640 (3)	0.0200 (9)
C13	0.24394 (9)	0.4900 (7)	0.3239 (3)	0.0208 (9)
H13	0.2539	0.3485	0.3007	0.025*
C14	0.21040 (9)	0.5242 (7)	0.3176 (2)	0.0190 (9)
H14	0.1973	0.4052	0.2906	0.023*
C15	0.18360 (9)	0.2525 (7)	0.1437 (2)	0.0185 (9)
C16	0.21888 (9)	0.2170 (6)	0.1269 (2)	0.0161 (8)
C17	0.23615 (10)	0.3835 (7)	0.0782 (3)	0.0208 (9)
H17	0.2252	0.5215	0.0556	0.025*
C18	0.26908 (9)	0.3478 (7)	0.0629 (3)	0.0207 (9)
H18	0.2807	0.4595	0.0289	0.025*
C19	0.28553 (10)	0.1471 (7)	0.0973 (3)	0.0205 (9)
C20	0.26838 (9)	−0.0176 (7)	0.1471 (3)	0.0202 (9)
H20	0.2794	−0.1528	0.1714	0.024*
C21	0.23526 (9)	0.0185 (7)	0.1606 (3)	0.0193 (9)
H21	0.2235	−0.0948	0.1936	0.023*
C22	0.08960 (9)	0.2800 (7)	0.1468 (3)	0.0202 (9)
C23	0.05331 (9)	0.2721 (6)	0.1396 (3)	0.0180 (8)
C24	0.03504 (9)	0.0837 (7)	0.1729 (3)	0.0194 (9)
H24	0.0461	−0.0504	0.1978	0.023*
C25	0.00123 (9)	0.0852 (7)	0.1709 (3)	0.0204 (9)
H25	−0.0109	−0.0450	0.1948	0.025*
C26	−0.01499 (9)	0.2800 (7)	0.1333 (3)	0.0196 (9)
C27	0.00314 (10)	0.4691 (7)	0.0973 (3)	0.0224 (9)
H27	−0.0079	0.5995	0.0703	0.027*
C28	0.03680 (10)	0.4672 (7)	0.1009 (3)	0.0213 (9)
H28	0.0490	0.5978	0.0773	0.026*
C29	0.12022 (9)	0.7557 (7)	0.8663 (3)	0.0192 (9)
C30	0.11696 (10)	0.7990 (7)	0.9555 (3)	0.0209 (9)
C31	0.14802 (11)	0.9108 (8)	0.9909 (3)	0.0231 (9)
C32	0.15734 (11)	1.1383 (8)	0.9436 (3)	0.0246 (9)
C33	0.15864 (10)	1.1010 (7)	0.8534 (3)	0.0222 (9)
C34	0.09532 (9)	0.2359 (7)	0.6377 (3)	0.0215 (9)
C35	0.09385 (12)	0.1929 (8)	0.5473 (3)	0.0270 (10)
C36	0.10020 (12)	0.4264 (8)	0.4982 (3)	0.0271 (10)
C37	0.13211 (11)	0.5451 (7)	0.5265 (3)	0.0239 (9)
C38	0.13258 (9)	0.5826 (7)	0.6174 (3)	0.0205 (9)
N1	0.11469 (8)	0.4256 (6)	0.6648 (2)	0.0199 (8)
N2	0.13975 (8)	0.9111 (6)	0.8214 (2)	0.0195 (8)
O1	0.08361 (7)	0.9522 (5)	0.37922 (18)	0.0231 (6)
O2	0.07864 (7)	0.6182 (5)	0.29949 (18)	0.0214 (6)
O3	−0.06926 (7)	0.7533 (5)	0.4067 (2)	0.0292 (7)
O4	0.14300 (7)	0.6199 (5)	0.3019 (2)	0.0259 (7)
O5	0.14794 (7)	0.9695 (5)	0.37326 (19)	0.0220 (6)
O6	0.29638 (7)	0.6388 (5)	0.3708 (2)	0.0285 (7)
O7	0.10601 (7)	0.4455 (5)	0.1152 (2)	0.0262 (7)
O8	0.10256 (7)	0.0995 (5)	0.1883 (2)	0.0263 (7)
O9	−0.04817 (7)	0.2972 (5)	0.1300 (2)	0.0281 (7)
O10	0.16759 (6)	0.1059 (5)	0.18552 (18)	0.0223 (6)
O11	0.17053 (7)	0.4496 (5)	0.11090 (19)	0.0240 (7)
O12	0.31774 (7)	0.1210 (5)	0.0800 (2)	0.0266 (7)
O13	0.14840 (7)	0.7485 (5)	0.65090 (19)	0.0264 (7)
O14	0.08108 (7)	0.1076 (5)	0.68791 (18)	0.0257 (7)
O15	0.10583 (7)	0.5882 (5)	0.82977 (18)	0.0271 (7)
O16	0.17485 (7)	1.2258 (5)	0.80592 (19)	0.0286 (7)
H1N	0.1135 (10)	0.456 (7)	0.717 (3)	0.023 (12)*
H2N	0.1428 (13)	0.884 (10)	0.765 (4)	0.059 (17)*
H2O	0.1035 (14)	0.639 (9)	0.301 (4)	0.061 (17)*
H3O	−0.0810 (13)	0.635 (9)	0.376 (4)	0.053 (16)*
H5O	0.1256 (12)	0.966 (7)	0.375 (3)	0.034 (13)*
H6O	0.3030 (11)	0.493 (8)	0.345 (3)	0.031 (13)*
H8O	0.1235 (13)	0.109 (8)	0.186 (4)	0.050 (16)*
H9O	−0.0564 (12)	0.179 (9)	0.156 (3)	0.041 (15)*
H11O	0.1471 (15)	0.460 (10)	0.117 (4)	0.070 (19)*
H12O	0.3243 (13)	0.008 (10)	0.105 (4)	0.051 (18)*
H30A	0.0967 (11)	0.922 (7)	0.964 (3)	0.033 (12)*
H30B	0.1107 (11)	0.652 (8)	0.982 (3)	0.038 (13)*
H31A	0.1458 (9)	0.949 (6)	1.049 (3)	0.011 (9)*
H31B	0.1676 (12)	0.785 (8)	0.986 (3)	0.044 (14)*
H32A	0.1417 (12)	1.261 (8)	0.954 (3)	0.042 (14)*
H32B	0.1780 (11)	1.218 (7)	0.960 (3)	0.030 (12)*
H35A	0.1115 (12)	0.074 (8)	0.534 (3)	0.044 (14)*
H35B	0.0698 (15)	0.117 (9)	0.533 (4)	0.067 (18)*
H36A	0.1018 (10)	0.393 (7)	0.437 (3)	0.020 (11)*
H36B	0.0800 (11)	0.539 (7)	0.508 (3)	0.029 (12)*
H37A	0.1514 (13)	0.426 (8)	0.511 (3)	0.049 (15)*
H37B	0.1358 (12)	0.714 (9)	0.498 (3)	0.047 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.019 (2)	0.021 (2)	0.017 (2)	0.0007 (15)	−0.0001 (17)	0.0007 (17)
C2	0.016 (2)	0.020 (2)	0.018 (2)	0.0011 (14)	−0.0018 (17)	0.0022 (17)
C3	0.024 (2)	0.018 (2)	0.022 (2)	0.0007 (15)	−0.0011 (19)	−0.0044 (17)
C4	0.023 (2)	0.017 (2)	0.023 (2)	−0.0031 (14)	−0.0036 (18)	−0.0021 (17)
C5	0.018 (2)	0.026 (2)	0.018 (2)	−0.0018 (15)	−0.0011 (18)	−0.0031 (17)
C6	0.024 (2)	0.024 (2)	0.026 (2)	0.0014 (16)	−0.0001 (19)	−0.0094 (18)
C7	0.025 (2)	0.020 (2)	0.024 (2)	−0.0013 (15)	−0.0023 (19)	−0.0034 (18)
C8	0.020 (2)	0.021 (2)	0.016 (2)	−0.0013 (15)	0.0011 (18)	0.0026 (17)
C9	0.019 (2)	0.017 (2)	0.015 (2)	−0.0002 (14)	0.0014 (16)	0.0053 (16)
C10	0.024 (2)	0.016 (2)	0.023 (2)	0.0014 (14)	0.0007 (19)	−0.0029 (17)
C11	0.022 (2)	0.021 (2)	0.028 (2)	−0.0060 (16)	−0.0040 (19)	−0.0016 (19)
C12	0.019 (2)	0.019 (2)	0.022 (2)	0.0008 (14)	−0.0020 (19)	0.0006 (17)
C13	0.023 (2)	0.0149 (19)	0.025 (2)	0.0019 (14)	0.0009 (19)	−0.0011 (17)
C14	0.022 (2)	0.021 (2)	0.014 (2)	−0.0038 (15)	−0.0006 (17)	−0.0048 (16)
C15	0.021 (2)	0.022 (2)	0.012 (2)	0.0009 (15)	−0.0025 (18)	−0.0025 (16)
C16	0.018 (2)	0.0161 (19)	0.0141 (19)	0.0025 (14)	−0.0036 (16)	−0.0018 (16)
C17	0.026 (2)	0.016 (2)	0.020 (2)	0.0020 (14)	−0.0023 (18)	0.0017 (17)
C18	0.020 (2)	0.017 (2)	0.025 (2)	−0.0017 (14)	0.0011 (18)	0.0024 (17)
C19	0.021 (2)	0.021 (2)	0.019 (2)	−0.0004 (15)	−0.0006 (18)	−0.0018 (17)
C20	0.023 (2)	0.017 (2)	0.021 (2)	0.0025 (15)	−0.0018 (18)	0.0036 (17)
C21	0.020 (2)	0.022 (2)	0.016 (2)	−0.0027 (15)	0.0024 (17)	−0.0004 (17)
C22	0.022 (2)	0.023 (2)	0.016 (2)	0.0024 (15)	0.0027 (18)	−0.0001 (17)
C23	0.020 (2)	0.019 (2)	0.014 (2)	0.0028 (14)	0.0002 (17)	−0.0030 (16)
C24	0.022 (2)	0.018 (2)	0.019 (2)	0.0028 (14)	−0.0027 (18)	−0.0010 (17)
C25	0.021 (2)	0.021 (2)	0.019 (2)	−0.0028 (15)	0.0003 (18)	0.0003 (17)
C26	0.016 (2)	0.025 (2)	0.019 (2)	−0.0021 (14)	−0.0005 (18)	−0.0037 (17)
C27	0.025 (2)	0.017 (2)	0.025 (2)	0.0041 (15)	−0.0030 (19)	0.0035 (18)
C28	0.024 (2)	0.019 (2)	0.021 (2)	−0.0027 (15)	0.0008 (19)	0.0037 (17)
C29	0.0136 (19)	0.024 (2)	0.020 (2)	−0.0009 (14)	−0.0009 (17)	0.0042 (18)
C30	0.022 (2)	0.020 (2)	0.021 (2)	0.0000 (15)	0.0045 (18)	0.0039 (18)
C31	0.027 (2)	0.027 (2)	0.015 (2)	0.0025 (16)	−0.0023 (19)	−0.0047 (18)
C32	0.025 (2)	0.023 (2)	0.025 (2)	−0.0031 (17)	0.000 (2)	−0.0043 (19)
C33	0.017 (2)	0.017 (2)	0.033 (2)	−0.0011 (15)	0.0014 (19)	0.0011 (18)
C34	0.019 (2)	0.020 (2)	0.026 (2)	0.0039 (15)	−0.0025 (19)	−0.0011 (18)
C35	0.037 (3)	0.022 (2)	0.022 (2)	0.0000 (19)	−0.003 (2)	−0.0013 (19)
C36	0.038 (3)	0.026 (2)	0.017 (2)	0.0016 (18)	−0.004 (2)	−0.0027 (18)
C37	0.034 (3)	0.021 (2)	0.017 (2)	0.0050 (17)	0.0030 (19)	0.0020 (18)
C38	0.016 (2)	0.022 (2)	0.024 (2)	0.0037 (15)	0.0009 (18)	0.0033 (18)
N1	0.0195 (19)	0.0241 (19)	0.0160 (19)	−0.0053 (12)	−0.0005 (15)	−0.0004 (15)
N2	0.0192 (19)	0.0248 (19)	0.0144 (19)	−0.0043 (13)	−0.0014 (15)	−0.0014 (15)
O1	0.0218 (16)	0.0263 (15)	0.0211 (16)	−0.0032 (11)	−0.0004 (13)	−0.0037 (13)
O2	0.0195 (16)	0.0232 (15)	0.0214 (16)	0.0007 (10)	0.0008 (13)	−0.0064 (12)
O3	0.0183 (15)	0.0314 (16)	0.0381 (19)	−0.0031 (12)	0.0025 (14)	−0.0147 (14)
O4	0.0181 (15)	0.0297 (16)	0.0298 (17)	0.0009 (11)	−0.0025 (13)	−0.0058 (14)
O5	0.0190 (16)	0.0251 (15)	0.0218 (16)	0.0034 (11)	0.0016 (13)	−0.0015 (13)
O6	0.0187 (16)	0.0240 (16)	0.043 (2)	0.0023 (11)	−0.0038 (15)	−0.0062 (15)
O7	0.0209 (16)	0.0273 (16)	0.0305 (18)	−0.0027 (11)	−0.0011 (14)	0.0087 (14)
O8	0.0175 (16)	0.0304 (17)	0.0311 (18)	0.0037 (12)	0.0031 (14)	0.0082 (14)
O9	0.0169 (15)	0.0271 (16)	0.040 (2)	−0.0027 (11)	−0.0040 (14)	0.0055 (15)
O10	0.0187 (15)	0.0272 (16)	0.0210 (16)	−0.0005 (11)	0.0005 (13)	0.0028 (13)
O11	0.0201 (17)	0.0255 (16)	0.0265 (17)	0.0054 (11)	0.0003 (14)	0.0055 (13)
O12	0.0163 (16)	0.0283 (17)	0.0351 (19)	0.0028 (11)	0.0023 (14)	0.0100 (15)
O13	0.0264 (16)	0.0280 (16)	0.0248 (17)	−0.0090 (12)	−0.0006 (14)	0.0013 (13)
O14	0.0269 (16)	0.0261 (16)	0.0242 (17)	−0.0087 (11)	−0.0001 (14)	0.0024 (13)
O15	0.0269 (16)	0.0299 (17)	0.0246 (17)	−0.0110 (12)	−0.0015 (14)	−0.0015 (13)
O16	0.0289 (17)	0.0290 (16)	0.0279 (17)	−0.0105 (12)	0.0024 (14)	0.0015 (13)

Geometric parameters (Å, º)

C1—O1	1.238 (5)	C24—C25	1.376 (5)
C1—O2	1.325 (4)	C24—H24	0.9500
C1—C2	1.474 (5)	C25—C26	1.394 (5)
C2—C7	1.394 (6)	C25—H25	0.9500
C2—C3	1.398 (5)	C26—O9	1.354 (4)
C3—C4	1.380 (5)	C26—C27	1.398 (5)
C3—H3	0.9500	C27—C28	1.371 (6)
C4—C5	1.388 (5)	C27—H27	0.9500
C4—H4	0.9500	C28—H28	0.9500
C5—O3	1.361 (5)	C29—O15	1.239 (4)
C5—C6	1.391 (5)	C29—N2	1.375 (5)
C6—C7	1.379 (5)	C29—C30	1.483 (6)
C6—H6	0.9500	C30—C31	1.519 (6)
C7—H7	0.9500	C30—H30A	1.07 (4)
C8—O4	1.235 (5)	C30—H30B	0.94 (5)
C8—O5	1.320 (5)	C31—C32	1.510 (6)
C8—C9	1.473 (5)	C31—H31A	0.98 (4)
C9—C10	1.391 (5)	C31—H31B	1.05 (5)
C9—C14	1.401 (5)	C32—C33	1.490 (6)
C10—C11	1.389 (6)	C32—H32A	0.94 (5)
C10—H10	0.9500	C32—H32B	0.98 (4)
C11—C12	1.388 (5)	C33—O16	1.225 (5)
C11—H11	0.9500	C33—N2	1.392 (5)
C12—O6	1.364 (5)	C34—O14	1.224 (5)
C12—C13	1.387 (5)	C34—N1	1.374 (5)
C13—C14	1.382 (5)	C34—C35	1.498 (6)
C13—H13	0.9500	C35—C36	1.528 (6)
C14—H14	0.9500	C35—H35A	1.00 (5)
C15—O10	1.237 (5)	C35—H35B	1.09 (6)
C15—O11	1.314 (5)	C36—C37	1.523 (6)
C15—C16	1.475 (5)	C36—H36A	1.02 (5)
C16—C21	1.385 (5)	C36—H36B	1.04 (4)
C16—C17	1.398 (6)	C37—C38	1.500 (6)
C17—C18	1.377 (5)	C37—H37A	1.05 (5)
C17—H17	0.9500	C37—H37B	1.04 (5)
C18—C19	1.401 (5)	C38—O13	1.238 (5)
C18—H18	0.9500	C38—N1	1.365 (5)
C19—O12	1.348 (5)	N1—H1N	0.87 (5)
C19—C20	1.400 (5)	N2—H2N	0.94 (6)
C20—C21	1.380 (5)	O2—H2O	1.02 (6)
C20—H20	0.9500	O3—H3O	0.94 (5)
C21—H21	0.9500	O5—H5O	0.91 (5)
C22—O7	1.236 (5)	O6—H6O	0.94 (4)
C22—O8	1.306 (5)	O8—H8O	0.86 (5)
C22—C23	1.482 (5)	O9—H9O	0.84 (5)
C23—C24	1.380 (5)	O11—H11O	0.96 (6)
C23—C28	1.408 (5)	O12—H12O	0.78 (5)
O1—C1—O2	122.7 (4)	C24—C25—H25	120.4
O1—C1—C2	122.2 (3)	C26—C25—H25	120.4
O2—C1—C2	115.1 (3)	O9—C26—C25	122.8 (3)
C7—C2—C3	119.6 (4)	O9—C26—C27	117.3 (3)
C7—C2—C1	119.0 (3)	C25—C26—C27	119.9 (3)
C3—C2—C1	121.5 (3)	C28—C27—C26	120.2 (3)
C4—C3—C2	120.2 (4)	C28—C27—H27	119.9
C4—C3—H3	119.9	C26—C27—H27	119.9
C2—C3—H3	119.9	C27—C28—C23	120.1 (3)
C3—C4—C5	119.8 (3)	C27—C28—H28	119.9
C3—C4—H4	120.1	C23—C28—H28	119.9
C5—C4—H4	120.1	O15—C29—N2	118.0 (4)
O3—C5—C4	122.0 (3)	O15—C29—C30	123.3 (4)
O3—C5—C6	117.6 (3)	N2—C29—C30	118.7 (4)
C4—C5—C6	120.4 (4)	C29—C30—C31	111.4 (4)
C7—C6—C5	119.9 (4)	C29—C30—H30A	107 (3)
C7—C6—H6	120.0	C31—C30—H30A	110 (2)
C5—C6—H6	120.0	C29—C30—H30B	110 (3)
C6—C7—C2	120.2 (3)	C31—C30—H30B	113 (3)
C6—C7—H7	119.9	H30A—C30—H30B	105 (4)
C2—C7—H7	119.9	C32—C31—C30	110.1 (4)
O4—C8—O5	122.9 (4)	C32—C31—H31A	110 (2)
O4—C8—C9	122.0 (4)	C30—C31—H31A	112 (2)
O5—C8—C9	115.1 (3)	C32—C31—H31B	108 (3)
C10—C9—C14	119.2 (4)	C30—C31—H31B	110 (3)
C10—C9—C8	122.2 (3)	H31A—C31—H31B	106 (4)
C14—C9—C8	118.6 (3)	C33—C32—C31	113.8 (4)
C11—C10—C9	120.5 (3)	C33—C32—H32A	108 (3)
C11—C10—H10	119.8	C31—C32—H32A	109 (3)
C9—C10—H10	119.8	C33—C32—H32B	107 (3)
C12—C11—C10	119.6 (3)	C31—C32—H32B	116 (3)
C12—C11—H11	120.2	H32A—C32—H32B	102 (4)
C10—C11—H11	120.2	O16—C33—N2	118.1 (4)
O6—C12—C13	122.2 (3)	O16—C33—C32	124.8 (4)
O6—C12—C11	117.4 (3)	N2—C33—C32	117.0 (4)
C13—C12—C11	120.4 (4)	O14—C34—N1	119.1 (4)
C14—C13—C12	120.0 (4)	O14—C34—C35	123.6 (4)
C14—C13—H13	120.0	N1—C34—C35	117.3 (4)
C12—C13—H13	120.0	C34—C35—C36	112.5 (4)
C13—C14—C9	120.3 (3)	C34—C35—H35A	107 (3)
C13—C14—H14	119.9	C36—C35—H35A	108 (3)
C9—C14—H14	119.9	C34—C35—H35B	108 (3)
O10—C15—O11	122.8 (4)	C36—C35—H35B	111 (3)
O10—C15—C16	122.1 (3)	H35A—C35—H35B	111 (4)
O11—C15—C16	115.2 (3)	C37—C36—C35	109.7 (4)
C21—C16—C17	119.5 (4)	C37—C36—H36A	109 (2)
C21—C16—C15	119.8 (3)	C35—C36—H36A	112 (2)
C17—C16—C15	120.7 (3)	C37—C36—H36B	112 (2)
C18—C17—C16	120.1 (4)	C35—C36—H36B	106 (2)
C18—C17—H17	120.0	H36A—C36—H36B	108 (3)
C16—C17—H17	120.0	C38—C37—C36	111.8 (4)
C17—C18—C19	120.2 (4)	C38—C37—H37A	108 (3)
C17—C18—H18	119.9	C36—C37—H37A	108 (3)
C19—C18—H18	119.9	C38—C37—H37B	109 (3)
O12—C19—C20	122.6 (3)	C36—C37—H37B	111 (3)
O12—C19—C18	117.6 (3)	H37A—C37—H37B	109 (4)
C20—C19—C18	119.8 (4)	O13—C38—N1	119.0 (4)
C21—C20—C19	119.2 (4)	O13—C38—C37	123.0 (4)
C21—C20—H20	120.4	N1—C38—C37	118.0 (4)
C19—C20—H20	120.4	C38—N1—C34	126.6 (4)
C20—C21—C16	121.2 (4)	C38—N1—H1N	118 (3)
C20—C21—H21	119.4	C34—N1—H1N	115 (3)
C16—C21—H21	119.4	C29—N2—C33	125.2 (4)
O7—C22—O8	123.3 (4)	C29—N2—H2N	120 (3)
O7—C22—C23	121.7 (3)	C33—N2—H2N	114 (3)
O8—C22—C23	114.9 (3)	C1—O2—H2O	107 (3)
C24—C23—C28	118.8 (3)	C5—O3—H3O	113 (3)
C24—C23—C22	121.8 (3)	C8—O5—H5O	111 (3)
C28—C23—C22	119.3 (3)	C12—O6—H6O	109 (3)
C25—C24—C23	121.6 (4)	C22—O8—H8O	110 (3)
C25—C24—H24	119.2	C26—O9—H9O	109 (3)
C23—C24—H24	119.2	C15—O11—H11O	114 (3)
C24—C25—C26	119.3 (3)	C19—O12—H12O	108 (4)
O1—C1—C2—C7	2.9 (6)	C18—C19—C20—C21	1.0 (6)
O2—C1—C2—C7	−177.7 (4)	C19—C20—C21—C16	−1.2 (6)
O1—C1—C2—C3	−177.7 (4)	C17—C16—C21—C20	0.2 (6)
O2—C1—C2—C3	1.7 (6)	C15—C16—C21—C20	−179.0 (4)
C7—C2—C3—C4	−0.6 (6)	O7—C22—C23—C24	178.1 (4)
C1—C2—C3—C4	−180.0 (4)	O8—C22—C23—C24	−1.6 (6)
C2—C3—C4—C5	0.2 (6)	O7—C22—C23—C28	−4.7 (6)
C3—C4—C5—O3	−179.0 (4)	O8—C22—C23—C28	175.7 (4)
C3—C4—C5—C6	0.4 (6)	C28—C23—C24—C25	−1.6 (6)
O3—C5—C6—C7	178.9 (4)	C22—C23—C24—C25	175.6 (4)
C4—C5—C6—C7	−0.5 (6)	C23—C24—C25—C26	1.0 (6)
C5—C6—C7—C2	0.1 (6)	C24—C25—C26—O9	−178.8 (4)
C3—C2—C7—C6	0.4 (6)	C24—C25—C26—C27	0.8 (6)
C1—C2—C7—C6	179.9 (4)	O9—C26—C27—C28	177.7 (4)
O4—C8—C9—C10	179.4 (4)	C25—C26—C27—C28	−1.8 (6)
O5—C8—C9—C10	−0.7 (6)	C26—C27—C28—C23	1.2 (6)
O4—C8—C9—C14	−0.2 (6)	C24—C23—C28—C27	0.5 (6)
O5—C8—C9—C14	179.7 (4)	C22—C23—C28—C27	−176.8 (4)
C14—C9—C10—C11	1.8 (6)	O15—C29—C30—C31	150.0 (4)
C8—C9—C10—C11	−177.8 (4)	N2—C29—C30—C31	−31.1 (5)
C9—C10—C11—C12	0.4 (6)	C29—C30—C31—C32	53.5 (5)
C10—C11—C12—O6	178.5 (4)	C30—C31—C32—C33	−50.9 (5)
C10—C11—C12—C13	−2.1 (6)	C31—C32—C33—O16	−155.8 (4)
O6—C12—C13—C14	−179.0 (4)	C31—C32—C33—N2	24.7 (5)
C11—C12—C13—C14	1.6 (6)	O14—C34—C35—C36	155.0 (4)
C12—C13—C14—C9	0.6 (6)	N1—C34—C35—C36	−27.2 (6)
C10—C9—C14—C13	−2.3 (6)	C34—C35—C36—C37	52.5 (5)
C8—C9—C14—C13	177.3 (4)	C35—C36—C37—C38	−52.6 (5)
O10—C15—C16—C21	−2.0 (6)	C36—C37—C38—O13	−151.8 (4)
O11—C15—C16—C21	178.1 (4)	C36—C37—C38—N1	28.2 (5)
O10—C15—C16—C17	178.8 (4)	O13—C38—N1—C34	178.6 (4)
O11—C15—C16—C17	−1.0 (6)	C37—C38—N1—C34	−1.5 (6)
C21—C16—C17—C18	1.0 (6)	O14—C34—N1—C38	178.8 (4)
C15—C16—C17—C18	−179.8 (4)	C35—C34—N1—C38	0.9 (6)
C16—C17—C18—C19	−1.2 (6)	O15—C29—N2—C33	−177.1 (4)
C17—C18—C19—O12	179.9 (4)	C30—C29—N2—C33	4.0 (6)
C17—C18—C19—C20	0.2 (6)	O16—C33—N2—C29	−179.8 (4)
O12—C19—C20—C21	−178.7 (4)	C32—C33—N2—C29	−0.3 (6)

(GM-35DHBA)

Crystal data

C7H6O4·C5H7NO2	Z = 2
Mr = 267.23	F(000) = 280
Triclinic, P1	Dx = 1.494 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6761 (3) Å	Cell parameters from 8252 reflections
b = 9.1128 (4) Å	θ = 3.3–30.1°
c = 10.9447 (4) Å	µ = 0.12 mm^−1
α = 93.397 (3)°	T = 100 K
β = 107.694 (3)°	Block, colourless
γ = 108.173 (4)°	0.24 × 0.22 × 0.20 mm
V = 593.92 (5) Å^3

Data collection

Four-circle diffractometer	2329 independent reflections
Radiation source: Mova (Mo) X-ray Source	Rint = 0.031
Mirror monochromator	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies, Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET) (compiled Jan 14 2014,18:38:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −8→8
Tmin = 0.841, Tmax = 1.000	k = −11→11
11839 measured reflections	l = −13→13

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0468P)^2 + 0.1835P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
2329 reflections	Δρmax = 0.26 e Å^−3
212 parameters	Δρmin = −0.21 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C1	0.45954 (18)	1.19843 (13)	0.70572 (10)	0.0142 (2)
C2	0.24590 (18)	1.07724 (13)	0.70006 (10)	0.0135 (2)
C3	0.15543 (19)	0.93734 (13)	0.61184 (10)	0.0138 (2)
H3	0.2313	0.9158	0.5561	0.017*
C4	−0.04910 (18)	0.82974 (13)	0.60721 (10)	0.0140 (2)
C5	−0.15994 (18)	0.86142 (13)	0.68862 (11)	0.0150 (2)
H5	−0.3000	0.7877	0.6838	0.018*
C6	−0.06628 (19)	1.00086 (13)	0.77722 (11)	0.0144 (2)
C7	0.13857 (19)	1.10988 (13)	0.78395 (11)	0.0145 (2)
H7	0.2040	1.2049	0.8447	0.017*
C8	−0.05943 (19)	0.50595 (13)	0.27529 (11)	0.0143 (2)
C9	−0.29426 (19)	0.40960 (14)	0.26388 (12)	0.0162 (3)
C10	−0.43280 (19)	0.32214 (14)	0.12572 (11)	0.0170 (3)
C11	−0.30912 (19)	0.22792 (13)	0.07950 (11)	0.0153 (2)
C12	−0.07691 (18)	0.32979 (13)	0.09069 (11)	0.0139 (2)
N1	0.02769 (16)	0.46033 (11)	0.18822 (9)	0.0148 (2)
O1	0.54761 (13)	1.32048 (9)	0.78454 (8)	0.0175 (2)
O2	0.54367 (14)	1.16248 (10)	0.61820 (8)	0.0182 (2)
O3	−0.15073 (14)	0.69014 (9)	0.52418 (8)	0.0179 (2)
O4	−0.18242 (14)	1.02460 (10)	0.85444 (8)	0.0194 (2)
O5	0.05505 (13)	0.62391 (9)	0.35880 (8)	0.0175 (2)
O6	0.02443 (14)	0.30476 (10)	0.02066 (8)	0.0184 (2)
H1N	0.170 (3)	0.5229 (19)	0.1952 (15)	0.028 (4)*
H2O	0.670 (3)	1.235 (2)	0.6290 (16)	0.030 (4)*
H3O	−0.078 (3)	0.6801 (19)	0.4761 (17)	0.033 (4)*
H4O	−0.113 (3)	1.114 (2)	0.9064 (17)	0.036 (4)*
H9A	−0.281 (2)	0.3348 (16)	0.3251 (13)	0.017 (3)*
H9B	−0.357 (2)	0.4804 (18)	0.2971 (14)	0.026 (4)*
H10A	−0.578 (2)	0.2551 (17)	0.1233 (13)	0.020 (3)*
H10B	−0.453 (2)	0.3969 (18)	0.0689 (14)	0.024 (4)*
H11A	−0.292 (2)	0.1484 (16)	0.1349 (13)	0.017 (3)*
H11B	−0.388 (2)	0.1740 (16)	−0.0110 (14)	0.019 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0153 (6)	0.0152 (6)	0.0127 (5)	0.0068 (4)	0.0040 (4)	0.0030 (4)
C2	0.0143 (5)	0.0138 (6)	0.0125 (5)	0.0060 (4)	0.0032 (4)	0.0037 (4)
C3	0.0154 (5)	0.0157 (6)	0.0118 (5)	0.0070 (4)	0.0052 (4)	0.0026 (4)
C4	0.0158 (5)	0.0127 (5)	0.0120 (5)	0.0049 (4)	0.0027 (4)	0.0010 (4)
C5	0.0130 (5)	0.0149 (6)	0.0151 (5)	0.0026 (4)	0.0045 (4)	0.0020 (4)
C6	0.0155 (5)	0.0169 (6)	0.0125 (5)	0.0074 (5)	0.0054 (4)	0.0030 (4)
C7	0.0159 (5)	0.0124 (5)	0.0130 (5)	0.0042 (4)	0.0027 (4)	0.0000 (4)
C8	0.0174 (6)	0.0124 (5)	0.0148 (5)	0.0067 (4)	0.0060 (4)	0.0035 (4)
C9	0.0152 (6)	0.0153 (6)	0.0197 (6)	0.0053 (5)	0.0087 (5)	0.0012 (5)
C10	0.0135 (5)	0.0184 (6)	0.0186 (6)	0.0049 (5)	0.0055 (5)	0.0028 (5)
C11	0.0149 (5)	0.0147 (6)	0.0132 (5)	0.0028 (4)	0.0033 (4)	0.0003 (4)
C12	0.0156 (6)	0.0138 (5)	0.0127 (5)	0.0066 (4)	0.0038 (4)	0.0025 (4)
N1	0.0132 (5)	0.0132 (5)	0.0169 (5)	0.0021 (4)	0.0064 (4)	0.0000 (4)
O1	0.0169 (4)	0.0150 (4)	0.0178 (4)	0.0016 (3)	0.0069 (3)	−0.0015 (3)
O2	0.0162 (4)	0.0172 (4)	0.0195 (4)	0.0012 (4)	0.0095 (3)	−0.0016 (3)
O3	0.0188 (4)	0.0145 (4)	0.0180 (4)	0.0011 (3)	0.0092 (3)	−0.0042 (3)
O4	0.0176 (4)	0.0188 (4)	0.0201 (4)	0.0017 (3)	0.0104 (4)	−0.0047 (3)
O5	0.0183 (4)	0.0140 (4)	0.0190 (4)	0.0026 (3)	0.0087 (3)	−0.0024 (3)
O6	0.0181 (4)	0.0192 (4)	0.0175 (4)	0.0054 (3)	0.0078 (3)	−0.0019 (3)

Geometric parameters (Å, º)

C1—O1	1.2235 (13)	C6—C7	1.3947 (16)
C1—O2	1.3210 (13)	C8—O5	1.2335 (14)
C1—C2	1.4877 (15)	C8—N1	1.3638 (15)
C2—C3	1.3934 (16)	C8—C9	1.5013 (15)
C2—C7	1.3948 (16)	C9—C10	1.5246 (16)
C3—C4	1.3948 (16)	C10—C11	1.5230 (16)
C4—O3	1.3618 (13)	C11—C12	1.5012 (15)
C4—C5	1.3886 (16)	C12—O6	1.2198 (14)
C5—C6	1.3913 (16)	C12—N1	1.3858 (14)
C6—O4	1.3578 (14)
O1—C1—O2	123.47 (10)	C5—C6—C7	120.11 (10)
O1—C1—C2	122.48 (10)	C6—C7—C2	118.98 (10)
O2—C1—C2	114.05 (9)	O5—C8—N1	119.41 (10)
C3—C2—C7	121.56 (10)	O5—C8—C9	122.74 (10)
C3—C2—C1	120.63 (10)	N1—C8—C9	117.85 (10)
C7—C2—C1	117.80 (10)	C8—C9—C10	111.95 (9)
C2—C3—C4	118.46 (10)	C11—C10—C9	109.62 (10)
O3—C4—C5	116.55 (10)	C12—C11—C10	111.52 (9)
O3—C4—C3	122.71 (10)	O6—C12—N1	118.51 (10)
C5—C4—C3	120.73 (10)	O6—C12—C11	124.51 (10)
C4—C5—C6	120.14 (10)	N1—C12—C11	116.98 (9)
O4—C6—C5	117.31 (10)	C8—N1—C12	126.49 (10)
O4—C6—C7	122.58 (10)
O1—C1—C2—C3	−177.67 (11)	C5—C6—C7—C2	0.53 (17)
O2—C1—C2—C3	2.59 (15)	C3—C2—C7—C6	−1.27 (17)
O1—C1—C2—C7	3.47 (17)	C1—C2—C7—C6	177.58 (10)
O2—C1—C2—C7	−176.27 (10)	O5—C8—C9—C10	153.92 (11)
C7—C2—C3—C4	0.99 (17)	N1—C8—C9—C10	−25.49 (15)
C1—C2—C3—C4	−177.83 (10)	C8—C9—C10—C11	53.06 (13)
C2—C3—C4—O3	179.90 (10)	C9—C10—C11—C12	−54.94 (13)
C2—C3—C4—C5	0.03 (17)	C10—C11—C12—O6	−151.08 (11)
O3—C4—C5—C6	179.38 (10)	C10—C11—C12—N1	29.28 (14)
C3—C4—C5—C6	−0.75 (18)	O5—C8—N1—C12	178.68 (10)
C4—C5—C6—O4	−179.73 (10)	C9—C8—N1—C12	−1.89 (17)
C4—C5—C6—C7	0.46 (17)	O6—C12—N1—C8	−179.77 (10)
O4—C6—C7—C2	−179.27 (10)	C11—C12—N1—C8	−0.11 (17)