Cyclic hetero­tetra­meric and low-dimensional hydrogen-bonded polymeric structures in the morpholinium salts of ring-substituted benzoic acid analogues

The morpholinium (tetra­hydro-2H-1,4-oxazin-4-ium) cation has been used as a counter-ion in both inorganic and organic salt formation and particularly in metal complex stabilization. To examine the influence of inter­active substituent groups in the aromatic rings of benzoic acids upon secondary structure generation, the anhydrous salts of morpholine with salicylic acid, C₄H₁₀NO⁺·C₇H₅O₃⁻, (I), 3,5-di­nitro­salicylic acid, C₄H₁₀NO⁺·C₇H₃N₂O₇⁻, (II), 3,5-di­nitro­benzoic acid, C₄H₁₀NO⁺·C₇H₃N₂O₆⁻, (III), and 4-nitro­anthranilic acid, C₄H₁₀NO⁺·C₇H₅N₂O₄⁻, (IV), have been prepared and their hydrogen-bonded crystal structures are described. In the crystal structures of (I), (III) and (IV), the cations and anions are linked by moderately strong N—H...O_carboxyl hydrogen bonds, but the secondary structure propagation differs among the three, viz. one-dimensional chains extending along [010] in (I), a discrete cyclic hetero­tetra­mer in (III), and in (IV), a hetero­tetra­mer with amine N—H...O hydrogen-bond extensions along b, giving a two-layered ribbon structure. With the hetero­tetra­mers in both (III) and (IV), the ion pairs are linked though inversion-related N—H...O_carboxylate hydrogen bonds, giving cyclic R₄⁴(12) motifs. With (II), in which the anion is a phenolate rather than a carboxyl­ate, the stronger assocation is through a symmetric lateral three-centre cyclic R₁²(6) N—H...(O,O′) hydrogen-bonding linkage involving the phenolate and nitro O-atom acceptors of the anion, with extension through a weaker O—H...O_carboxyl hydrogen bond. This results in a one-dimensional chain structure extending along [100]. In the structures of two of the salts [i.e. (II) and (IV)], there are also π–π ring inter­actions, with ring-centroid separations of 3.5516 (9) and 3.7700 (9) Å in (II), and 3.7340 (9) Å in (IV).

S1. Introduction

The morpholinium (tetra­hydro-2H-1,4-oxazin-4-ium) cation has a proven history as a counter-ion in both inorganic and organic salt formation and particularly in metal complex stabilization, e.g. bis­(morpholin-4-ium) tetra­chloro­cuprate(II) (Willett et al., 1988), with rare examples in which it acts as an O-donor ligand species in complex formation, e.g. in dinuclear hexachloridobis(morpholin-1-ium-κO)dicopper(II) (Scott et al., 1988). In the current Cambridge Structural Database (CSD, Version?; Groom & Allen, 2014), there are 209 entries for the morpholinium cation. Of particular inter­est to us are the morpholinium carboxyl­ate salts, which number only ca 23, among which are those which have been used as models in studies of active pharmaceutical ingredients (APIs), e.g. the acetate (Kelley et al., 2013), the 4-amino­salicylate (André et al., 2009), the mono­hydrogen tartrate (a monohydrate; Liu, 2012) and the di­hydrogen citrate (also a monohydrate; Chen et al., 2003). A rare 1:1 salt adduct with 4-meth­oxy­benzoic acid (a monohydrate) is also known (Feng & Zhao, 2011). However, commonly, anhydrous organic morpholine salts are formed.

The crystal structures of only eight anhydrous morpholinium salts of the substituted benzoic acid analogues have been reported, e.g. with 4-nitro­benzoic acid (Chumakov et al., 2006), 5-nitro­salicylic acid (Smith et al., 2005), 4-amino­salicylic acid (André et al., 2009) and a series of isomeric chloro­nitro­benzoates (2,4-, 2,5-, 4,2-, 4,3- and 5,2-; Ishida et al., 2001a,b,c). In these, cation–anion N—H···O hydrogen-bonding inter­actions commonly generate either one-dimensional hydrogen-bonded ribbons (structure Type 1) or discrete cyclic hydrogen-bonded cage structures (Type 2), featuring primarily the R₄⁴(12) ring motif [for graph-set nomenclature, see Bernstein et al. (1995)] (Type 2a), such as is present in the structure of N-methyl­anilinium 3,5-di­nitro­benzoate (Smith et al., 1998), or the less common R₄²(8) ring motif (Type 2b) (Fig. 1), found in the analogous morpholinium phen­oxy­acetates (Smith & Lynch, 2015).

Within the Type 1 structures, the ribbons comprise either the more common –A–A–/–B–B– sequences (Type 1a) or the –A–B–/–B–A– sequences (Type 1b). The less common 1b subtype is found in the structure of morpholinium 2-chloro-4-nitro­benzoate (Ishida et al., 2001a) and in morpholinium (4-fluoro­phen­oxy)­acetate (Smith & Lynch, 2015), both of which have the A–B sequence generated by a crystallographic 2₁ screw operation.

The linear Type 1a chain structure is also found in the related anhydrous morpholinium salt of cinnamic acid (Smith, 2015) and two of the four morpholinium salts of phen­oxy­acetic acid analogues (Smith & Lynch, 2015). The fourth salt of this series, with (2,4-di­chloro­phen­oxy)­acetic acid, has the cyclic Type 2b structure. Of chemical inter­est is also the Type 2a structure of morpholinium morpholine-4-carboxyl­ate (Brown & Gray, 1982; Von Dreele et al., 1983), a salt often readily formed in attempted preparations of morpholine salts and also by the reaction of morpholine with dry ice.

One structure among the few known anhydrous morpholine salts of the associatively substituted benzoic acids which constitutes a variant of the above-described Type 1 and Type 2 sets is found in the 5-nitro­salicylate (Smith et al., 2005). In this structure, both the cations and anions lie, respectively, across and within crystallographic mirror planes, and the primary association is a variant of the Type 2a subset but with an R₄³(10) motif, involving three rather than four carboxyl­ate O atoms and giving an overall three-dimensional structure.

To examine the influence of inter­active substituent groups in the aromatic rings of, specifically, the benzoic acids upon secondary structure generation, the morpholinium salts with salicylic acid (SA), (3,5-di­nitro­salicylic acid (DNSA), 3,5-di­nitro­benzoic acid (DNBA) and 4-nitro­anthranilic acid (NAA), namely the title salts morpholinium 2-hy­droxy­benzoate, (I), morpholinium 2-carb­oxy-4,6-di­nitro­phenolate, (II), morpholinium 3,5-di­nitro­benzoate, (III), and morpholinium 2-amino-4-nitro­benzoate, (IV), were prepared and their crystal structures and hydrogen-bonding modes are reported herein. Morpholinium salicylate, (I), has a history of medical applications, as retarcyl or depasol, used as an analgesic, an anti­pyretic and an anti-inflammatory agent (O'Neil, 2001). With DNSA, a large number of structures of Lewis base salts have been reported of which ca 70% are phenolates rather than carboxyl­ates (Smith et al., 2007). However, with NAA, there is only one example of an anhydrous Lewis base salt, that with di­cyclo­hexyl­amine (Smith et al., 2004).

S2. Experimental

S2.1. Synthesis and crystallization

The title compounds, (I)–(IV), were prepared by the dropwise addition of morpholine at room temperature to solutions of salicylic acid (140 mg), 3,5-di­nitro­salicylic acid (230 mg), 3,5-di­nitro­benzoic acid (210 mg) or 4-nitro­anthranilic acid (170 mg), respectively, in ethanol (10 ml). Room-temperature evaporation of the solutions gave either fine yellow needles of (II), colourless plates of (III) or orange plates of (IV), from which specimens were cleaved for the X-ray analyses. For (I), the same preparative procedure was employed using salicylic acid, but the final oil which resulted after solvent evaporation was redissolved in ethanol, finally giving thin colourless plates from which a specimen was cleaved for the X-ray analysis.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The aminium, phenolic or carb­oxy­lic acid H atoms were located in difference Fourier analyses and allowed to refine with distance restraints of N—H = 0.90 (2) Å and U_iso(H) = 1.2U_eq(N) or O—H = 0.90 (2) Å and U_iso(H) = 1.5U_eq(O). The remaining H atoms were placed in calculated positions with aromatic C—H = 0.95 Å or methyl­ene C—H = 0.99 Å, and allowed to ride in the refinements, with U_iso(H) = 1.2U_eq(C). In the refinement of (I), the Flack parameter (Flack, 1983) for this achiral molecule [0.2 (14) for 1201 Friedel pairs] is meaningless.

S3. Results and discussion

The asymmetric units of (I)–(IV) comprise a morpholinium cation (B) and a salicylate anion (A) in (I) (Fig. 2), a 2-carb­oxy-4,6-di­nitro­phenolate anion (A) in (II) (Fig. 3), a 2,4-di­nitro­benzoate anion (A) in (III) (Fig. 4) and a 4-nitro­anthranilate anion (A) in (IV) (Fig. 5). In the structures of (I), (III) and (IV), two moderately strong morpholinium N1B—H···OA_carboxyl hydrogen-bonding inter­actions are present [N···O range = 2.6855 (17)–2.7756 (17) Å, both in (IV)] (Tables 2, 4 and 5).

With (II), which is a phenolate rather than a carboxyl­ate, the single N···O_{carboxyl­ate} assocation is weaker [2.912 (2) Å] than the N1B···H···(O:O¹) inter­action through a symmetric three-centre R₁²(6) chelate association with the phenolate (O2A) and nitro O31A acceptors [2.790 (2) and 2.806 (2) Å, respectively] (Table 3). This primary lateral associative mode is also found in the structures of the morpholinium salts of 2,4-di­nitro­phenol (Majerz et al., 1996) and picric acid (Vembu & Fronczek, 2009; Refat et al., 2010). The hydrogen-bonding extensions in (I)–(IV) result in different overall structures, while inter-ring π–π associations are present in two of these [(II) and (IV)].

With the morpholinium salt of salicylic acid, (I), the primary cation–anion pairs (Fig. 1) are linked through an N1B—H···O12Aⁱ hydrogen bond (Table 2), generating one-dimensional ribbon structures extending along b (Fig. 6). These ribbons have the Type 1b subset structure (the alternating parallel A,B,A,B/B,A,B,A anion–cation sequence in the chain) rather than the more common Type 1a subset. Other Type 1b chain polymers are found in morpholinium 2-chloro-4-nitro­benzoate (Ishida et al., 2001a) and in morpholinium (3,5-di­chloro­phen­oxy)­acetate (Smith & Lynch, 2015), which like (I) are propagated along crystallographic 2₁ screw axes. Present also in the structure of (I) are minor weak inter­chain C—H···O inter­actions with the morpholinium and phenolate O-atom acceptors. No π–π ring inter­actions are present in the structure.

In the salicylate anion, the common short intra­molecular cyclic S6 carboxyl O—H···O_phenolate hydrogen bond is present, with the carboxyl­ate group rotated only slightly out of the benzene plane [torsion angle C2A—C1A—C11A—O12A = -172.2 (2)°].

In the structure of the morpholinium salt of DNSA, (II), since the primary strong N—H···O inter­action involves the phenolate and nitro O atoms of the DNSA anion rather than the second carboxyl O atom (Table 3), a variant of the Type 1b (A,B,A,B) chain structure is found, extending parallel to the a direction (Fig. 7). Present also in the crystal structure are π–π inter­actions, with benzene ring-centroid separations Cg···Cgⁱⁱⁱ of 3.5516 (9) Å and Cg···Cg^iv of 3.7700 (9) Å [symmetry codes: (iii) -x + 3/2, - y + 1/2, -z + 1/2; (iv) -x + 3/2, y, z]. There are also minor C—H···O inter­actions to morpholinium and carboxyl O-atom acceptors (Table 3).

The DNSA anion, like other DNSA phenolate anions having the anti-related carboxyl group, has the short intra­molecular S(6) carboxyl O—H···O_phenolate hydrogen bond and is close to coplanar with the benzene ring [torsion angle C2A—C1A—C11A—O12A = -177.39 (15)°], as is one of the nitro groups [C4A—C5A—N5A—O52A = 178.95 (16)°]. However, the hydrogen-bond associated N3A nitro group is significantly rotated [C2A—C3A—N3A—O32A = -160.26 (14)°].

In the DNBA salt, (III), the N1B—H···O12Aⁱ hydrogen bond generates a centrosymmetric hetero­tetra­meric Type 2a ring structure [graph set R₄⁴(12)] (Fig. 8; see Table 4 for symmetry code). This cyclic system is similar to that found in the structures of morpholinium 4-amino­salicylate (André et al., 2009) and in four of the five morpholinium salts with the isomeric chloro-nitro-substituted benzoic acids (2-chloro-5-nitro-, 4-chloro-2-nitro-, 4-chloro-3-nitro- and 5-chloro-2-nitro; Ishida et al., 2001b, 2001c). It is also found in the previously mentioned morpholinium morpholine-4-carboxyl­ate salt (Brown & Gray, 1982; Von Dreele et al., 1983). In (IV) [Should this be (III)?], weak C—H···O hydrogen bonds are also found, involving O_morpholine acceptors. No π–π inter­actions are present.

As is quite common with the DNBA cation, the carboxyl­ate group and the two nitro-substituent groups are essentially coplanar with the benzene ring [torsion angles: C2A—C1A—C11A—O12A = -171.3 (3)°; C2A—C3A—N3A—O32A = 179.3 (3)°; C4A—C5A—N5A—O52A = -178.0 (3)°].

With the structure of the NAA salt, (IV), the primary N1B—H···O12A hydrogen-bonded unit is linked by the second N1B—H···O11Aⁱ hydrogen-bonding inter­action (Table 5) into a centrosymmetric cyclic Type 2a hetero­tetra­mer substructure [graph set R₄⁴(12)]. The amino group of the anion expands the structure along [010] through an N1B—H···O11Aⁱⁱ hydrogen bond into a two-layered ribbon which lies parallel to (001) (Fig. 9; see Table 5 for symmetry code). A weak π–π inter­action Cg···Cgⁱⁱⁱ of 3.7340 (9) Å is found [symmetry code (iii) as above for salt (II)?], as well as a weak cation C—H···O_nitro hydrogen bond (Table 5). The second H atom of the amino group participates in an intra­molecular S(6) N—H···O hydrogen-bonding motif with a carboxyl O12A-atom acceptor, with the carboxyl group rotated slightly out of the benzene plane [torsion angle C6A—C1A—C11A—O12A = -161.96 (13)°], while the nitro group is close to coplanar with the ring [torsion angle C3A—C4A—N4A—O42A = -178.96 (13)°]. Unlike the hetero­tetra­mer in (III) which is essentially planar, in (IV) it is quite convoluted.

The structures of the morpholinium salts of the associatively substituted benzoic acid analogues reported here provide examples of both the common Type 1 and Type 2 hydrogen-bonded structures found among the anhydrous morpholinium salts, but the presence of associative substitutent groups influences the structure types, giving variants.

Structure description

The morpholinium (tetra­hydro-2H-1,4-oxazin-4-ium) cation has a proven history as a counter-ion in both inorganic and organic salt formation and particularly in metal complex stabilization, e.g. bis­(morpholin-4-ium) tetra­chloro­cuprate(II) (Willett et al., 1988), with rare examples in which it acts as an O-donor ligand species in complex formation, e.g. in dinuclear hexachloridobis(morpholin-1-ium-κO)dicopper(II) (Scott et al., 1988). In the current Cambridge Structural Database (CSD, Version?; Groom & Allen, 2014), there are 209 entries for the morpholinium cation. Of particular inter­est to us are the morpholinium carboxyl­ate salts, which number only ca 23, among which are those which have been used as models in studies of active pharmaceutical ingredients (APIs), e.g. the acetate (Kelley et al., 2013), the 4-amino­salicylate (André et al., 2009), the mono­hydrogen tartrate (a monohydrate; Liu, 2012) and the di­hydrogen citrate (also a monohydrate; Chen et al., 2003). A rare 1:1 salt adduct with 4-meth­oxy­benzoic acid (a monohydrate) is also known (Feng & Zhao, 2011). However, commonly, anhydrous organic morpholine salts are formed.

The crystal structures of only eight anhydrous morpholinium salts of the substituted benzoic acid analogues have been reported, e.g. with 4-nitro­benzoic acid (Chumakov et al., 2006), 5-nitro­salicylic acid (Smith et al., 2005), 4-amino­salicylic acid (André et al., 2009) and a series of isomeric chloro­nitro­benzoates (2,4-, 2,5-, 4,2-, 4,3- and 5,2-; Ishida et al., 2001a,b,c). In these, cation–anion N—H···O hydrogen-bonding inter­actions commonly generate either one-dimensional hydrogen-bonded ribbons (structure Type 1) or discrete cyclic hydrogen-bonded cage structures (Type 2), featuring primarily the R₄⁴(12) ring motif [for graph-set nomenclature, see Bernstein et al. (1995)] (Type 2a), such as is present in the structure of N-methyl­anilinium 3,5-di­nitro­benzoate (Smith et al., 1998), or the less common R₄²(8) ring motif (Type 2b) (Fig. 1), found in the analogous morpholinium phen­oxy­acetates (Smith & Lynch, 2015).

Within the Type 1 structures, the ribbons comprise either the more common –A–A–/–B–B– sequences (Type 1a) or the –A–B–/–B–A– sequences (Type 1b). The less common 1b subtype is found in the structure of morpholinium 2-chloro-4-nitro­benzoate (Ishida et al., 2001a) and in morpholinium (4-fluoro­phen­oxy)­acetate (Smith & Lynch, 2015), both of which have the A–B sequence generated by a crystallographic 2₁ screw operation.

The linear Type 1a chain structure is also found in the related anhydrous morpholinium salt of cinnamic acid (Smith, 2015) and two of the four morpholinium salts of phen­oxy­acetic acid analogues (Smith & Lynch, 2015). The fourth salt of this series, with (2,4-di­chloro­phen­oxy)­acetic acid, has the cyclic Type 2b structure. Of chemical inter­est is also the Type 2a structure of morpholinium morpholine-4-carboxyl­ate (Brown & Gray, 1982; Von Dreele et al., 1983), a salt often readily formed in attempted preparations of morpholine salts and also by the reaction of morpholine with dry ice.

One structure among the few known anhydrous morpholine salts of the associatively substituted benzoic acids which constitutes a variant of the above-described Type 1 and Type 2 sets is found in the 5-nitro­salicylate (Smith et al., 2005). In this structure, both the cations and anions lie, respectively, across and within crystallographic mirror planes, and the primary association is a variant of the Type 2a subset but with an R₄³(10) motif, involving three rather than four carboxyl­ate O atoms and giving an overall three-dimensional structure.

To examine the influence of inter­active substituent groups in the aromatic rings of, specifically, the benzoic acids upon secondary structure generation, the morpholinium salts with salicylic acid (SA), (3,5-di­nitro­salicylic acid (DNSA), 3,5-di­nitro­benzoic acid (DNBA) and 4-nitro­anthranilic acid (NAA), namely the title salts morpholinium 2-hy­droxy­benzoate, (I), morpholinium 2-carb­oxy-4,6-di­nitro­phenolate, (II), morpholinium 3,5-di­nitro­benzoate, (III), and morpholinium 2-amino-4-nitro­benzoate, (IV), were prepared and their crystal structures and hydrogen-bonding modes are reported herein. Morpholinium salicylate, (I), has a history of medical applications, as retarcyl or depasol, used as an analgesic, an anti­pyretic and an anti-inflammatory agent (O'Neil, 2001). With DNSA, a large number of structures of Lewis base salts have been reported of which ca 70% are phenolates rather than carboxyl­ates (Smith et al., 2007). However, with NAA, there is only one example of an anhydrous Lewis base salt, that with di­cyclo­hexyl­amine (Smith et al., 2004).

The asymmetric units of (I)–(IV) comprise a morpholinium cation (B) and a salicylate anion (A) in (I) (Fig. 2), a 2-carb­oxy-4,6-di­nitro­phenolate anion (A) in (II) (Fig. 3), a 2,4-di­nitro­benzoate anion (A) in (III) (Fig. 4) and a 4-nitro­anthranilate anion (A) in (IV) (Fig. 5). In the structures of (I), (III) and (IV), two moderately strong morpholinium N1B—H···OA_carboxyl hydrogen-bonding inter­actions are present [N···O range = 2.6855 (17)–2.7756 (17) Å, both in (IV)] (Tables 2, 4 and 5).

With (II), which is a phenolate rather than a carboxyl­ate, the single N···O_{carboxyl­ate} assocation is weaker [2.912 (2) Å] than the N1B···H···(O:O¹) inter­action through a symmetric three-centre R₁²(6) chelate association with the phenolate (O2A) and nitro O31A acceptors [2.790 (2) and 2.806 (2) Å, respectively] (Table 3). This primary lateral associative mode is also found in the structures of the morpholinium salts of 2,4-di­nitro­phenol (Majerz et al., 1996) and picric acid (Vembu & Fronczek, 2009; Refat et al., 2010). The hydrogen-bonding extensions in (I)–(IV) result in different overall structures, while inter-ring π–π associations are present in two of these [(II) and (IV)].

With the morpholinium salt of salicylic acid, (I), the primary cation–anion pairs (Fig. 1) are linked through an N1B—H···O12Aⁱ hydrogen bond (Table 2), generating one-dimensional ribbon structures extending along b (Fig. 6). These ribbons have the Type 1b subset structure (the alternating parallel A,B,A,B/B,A,B,A anion–cation sequence in the chain) rather than the more common Type 1a subset. Other Type 1b chain polymers are found in morpholinium 2-chloro-4-nitro­benzoate (Ishida et al., 2001a) and in morpholinium (3,5-di­chloro­phen­oxy)­acetate (Smith & Lynch, 2015), which like (I) are propagated along crystallographic 2₁ screw axes. Present also in the structure of (I) are minor weak inter­chain C—H···O inter­actions with the morpholinium and phenolate O-atom acceptors. No π–π ring inter­actions are present in the structure.

In the salicylate anion, the common short intra­molecular cyclic S6 carboxyl O—H···O_phenolate hydrogen bond is present, with the carboxyl­ate group rotated only slightly out of the benzene plane [torsion angle C2A—C1A—C11A—O12A = -172.2 (2)°].

In the structure of the morpholinium salt of DNSA, (II), since the primary strong N—H···O inter­action involves the phenolate and nitro O atoms of the DNSA anion rather than the second carboxyl O atom (Table 3), a variant of the Type 1b (A,B,A,B) chain structure is found, extending parallel to the a direction (Fig. 7). Present also in the crystal structure are π–π inter­actions, with benzene ring-centroid separations Cg···Cgⁱⁱⁱ of 3.5516 (9) Å and Cg···Cg^iv of 3.7700 (9) Å [symmetry codes: (iii) -x + 3/2, - y + 1/2, -z + 1/2; (iv) -x + 3/2, y, z]. There are also minor C—H···O inter­actions to morpholinium and carboxyl O-atom acceptors (Table 3).

The DNSA anion, like other DNSA phenolate anions having the anti-related carboxyl group, has the short intra­molecular S(6) carboxyl O—H···O_phenolate hydrogen bond and is close to coplanar with the benzene ring [torsion angle C2A—C1A—C11A—O12A = -177.39 (15)°], as is one of the nitro groups [C4A—C5A—N5A—O52A = 178.95 (16)°]. However, the hydrogen-bond associated N3A nitro group is significantly rotated [C2A—C3A—N3A—O32A = -160.26 (14)°].

In the DNBA salt, (III), the N1B—H···O12Aⁱ hydrogen bond generates a centrosymmetric hetero­tetra­meric Type 2a ring structure [graph set R₄⁴(12)] (Fig. 8; see Table 4 for symmetry code). This cyclic system is similar to that found in the structures of morpholinium 4-amino­salicylate (André et al., 2009) and in four of the five morpholinium salts with the isomeric chloro-nitro-substituted benzoic acids (2-chloro-5-nitro-, 4-chloro-2-nitro-, 4-chloro-3-nitro- and 5-chloro-2-nitro; Ishida et al., 2001b, 2001c). It is also found in the previously mentioned morpholinium morpholine-4-carboxyl­ate salt (Brown & Gray, 1982; Von Dreele et al., 1983). In (IV) [Should this be (III)?], weak C—H···O hydrogen bonds are also found, involving O_morpholine acceptors. No π–π inter­actions are present.

As is quite common with the DNBA cation, the carboxyl­ate group and the two nitro-substituent groups are essentially coplanar with the benzene ring [torsion angles: C2A—C1A—C11A—O12A = -171.3 (3)°; C2A—C3A—N3A—O32A = 179.3 (3)°; C4A—C5A—N5A—O52A = -178.0 (3)°].

With the structure of the NAA salt, (IV), the primary N1B—H···O12A hydrogen-bonded unit is linked by the second N1B—H···O11Aⁱ hydrogen-bonding inter­action (Table 5) into a centrosymmetric cyclic Type 2a hetero­tetra­mer substructure [graph set R₄⁴(12)]. The amino group of the anion expands the structure along [010] through an N1B—H···O11Aⁱⁱ hydrogen bond into a two-layered ribbon which lies parallel to (001) (Fig. 9; see Table 5 for symmetry code). A weak π–π inter­action Cg···Cgⁱⁱⁱ of 3.7340 (9) Å is found [symmetry code (iii) as above for salt (II)?], as well as a weak cation C—H···O_nitro hydrogen bond (Table 5). The second H atom of the amino group participates in an intra­molecular S(6) N—H···O hydrogen-bonding motif with a carboxyl O12A-atom acceptor, with the carboxyl group rotated slightly out of the benzene plane [torsion angle C6A—C1A—C11A—O12A = -161.96 (13)°], while the nitro group is close to coplanar with the ring [torsion angle C3A—C4A—N4A—O42A = -178.96 (13)°]. Unlike the hetero­tetra­mer in (III) which is essentially planar, in (IV) it is quite convoluted.

The structures of the morpholinium salts of the associatively substituted benzoic acid analogues reported here provide examples of both the common Type 1 and Type 2 hydrogen-bonded structures found among the anhydrous morpholinium salts, but the presence of associative substitutent groups influences the structure types, giving variants.

Synthesis and crystallization

The title compounds, (I)–(IV), were prepared by the dropwise addition of morpholine at room temperature to solutions of salicylic acid (140 mg), 3,5-di­nitro­salicylic acid (230 mg), 3,5-di­nitro­benzoic acid (210 mg) or 4-nitro­anthranilic acid (170 mg), respectively, in ethanol (10 ml). Room-temperature evaporation of the solutions gave either fine yellow needles of (II), colourless plates of (III) or orange plates of (IV), from which specimens were cleaved for the X-ray analyses. For (I), the same preparative procedure was employed using salicylic acid, but the final oil which resulted after solvent evaporation was redissolved in ethanol, finally giving thin colourless plates from which a specimen was cleaved for the X-ray analysis.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. The aminium, phenolic or carb­oxy­lic acid H atoms were located in difference Fourier analyses and allowed to refine with distance restraints of N—H = 0.90 (2) Å and U_iso(H) = 1.2U_eq(N) or O—H = 0.90 (2) Å and U_iso(H) = 1.5U_eq(O). The remaining H atoms were placed in calculated positions with aromatic C—H = 0.95 Å or methyl­ene C—H = 0.99 Å, and allowed to ride in the refinements, with U_iso(H) = 1.2U_eq(C). In the refinement of (I), the Flack parameter (Flack, 1983) for this achiral molecule [0.2 (14) for 1201 Friedel pairs] is meaningless.

Computing details

For all compounds, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. Classification of the structure types among known morpholinate salts of aromatic carboxylate salts
	Fig. 2. The atom-numbering scheme and the molecular conformation of the morpholinium cation (B) and the SA anion (A) in (I), with displacement ellipsoids drawn at the 40% probability level. The hydrogen bonds are shown as dashed lines.
	Fig. 3. The atom-numbering scheme and the molecular conformation of the morpholinium cation (B) and the DNSA anion (A) in (II), with displacement ellipsoids drawn at the 40% probability level. The hydrogen bonds are shown as dashed lines.
	Fig. 4. The atom-numbering scheme and the molecular conformation of the morpholinium cation (B) and the DNBA anion (A) in (III), with displacement ellipsoids drawn at the 40% probability level. The hydrogen bond is shown as a dashed line.
	Fig. 5. The atom-numbering scheme and the molecular conformation of the morpholinium cation (B) and the NAA anion (A) in (IV), with displacement ellipsoids drawn at the 40% probability level. The hydrogen bonds are shown as dashed lines.
	Fig. 6. The one-dimensional hydrogen-bonded polymeric structure of (I), extending along b. Non-interactive H atoms have been omitted. (For symmetry codes, see Table 2.)
	Fig. 7. The one-dimensional hydrogen-bonded polymeric structure of (II), extending along a. (For symmetry codes, see Table 3.)
	Fig. 8. The centrosymmetric cyclic hydrogen-bonded heterotetrameric structure of (III). (For symmetry codes, see Table 4.)
	Fig. 9. The two-layered hydrogen-bonded polymeric structure of (IV), based on a cyclic heterotetrameric core. (For symmetry codes, see Table 5.)

(I) Tetrahydro-2H-1,4-oxazin-4-ium 2-hydroxybenzoate

Crystal data

C4H10NO^+·C7H5O3^−	F(000) = 240
Mr = 225.24	Dx = 1.325 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 570 reflections
a = 6.7342 (10) Å	θ = 3.8–26.2°
b = 7.8271 (10) Å	µ = 0.10 mm^−1
c = 10.7822 (17) Å	T = 200 K
β = 96.442 (13)°	Plate, colourless
V = 564.73 (14) Å^3	0.35 × 0.25 × 0.12 mm
Z = 2

Data collection

Oxford Gemini-S CCD area-detector diffractometer	1735 independent reflections
Radiation source: Enhance (Mo) X-ray source	1484 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −7→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −9→8
Tmin = 0.886, Tmax = 0.980	l = −7→13
2061 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.091	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 0.006P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
1735 reflections	Δρmax = 0.13 e Å^−3
154 parameters	Δρmin = −0.17 e Å^−3
3 restraints	Absolute structure: Flack (1983), with 1201 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.2 (14)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
O2A	0.3375 (3)	0.8926 (2)	0.11941 (17)	0.0485 (7)
O11A	0.8519 (3)	0.6036 (3)	0.15121 (18)	0.0547 (7)
O12A	0.6669 (2)	0.8044 (3)	0.04968 (16)	0.0486 (6)
C1A	0.5667 (3)	0.7022 (3)	0.2387 (2)	0.0322 (8)
C2A	0.3878 (3)	0.7958 (4)	0.2227 (2)	0.0335 (7)
C3A	0.2564 (4)	0.7893 (4)	0.3122 (2)	0.0408 (8)
C4A	0.3033 (4)	0.6955 (3)	0.4188 (2)	0.0434 (9)
C5A	0.4790 (4)	0.6066 (4)	0.4382 (2)	0.0457 (9)
C6A	0.6093 (4)	0.6092 (4)	0.3482 (2)	0.0405 (9)
C11A	0.7067 (4)	0.7011 (3)	0.1409 (2)	0.0375 (9)
O4B	0.9619 (3)	0.1484 (2)	0.33754 (17)	0.0511 (7)
N1B	1.0591 (3)	0.3055 (3)	0.1168 (2)	0.0402 (7)
C2B	0.9180 (4)	0.1607 (4)	0.1130 (2)	0.0441 (9)
C3B	0.8174 (4)	0.1607 (4)	0.2308 (3)	0.0488 (10)
C5B	1.0945 (4)	0.2905 (4)	0.3436 (2)	0.0454 (9)
C6B	1.2045 (3)	0.2988 (5)	0.2310 (2)	0.0441 (9)
H2A	0.438 (3)	0.886 (4)	0.074 (2)	0.0730*
H3A	0.13350	0.84990	0.29990	0.0490*
H4A	0.21240	0.69200	0.48010	0.0520*
H5A	0.51100	0.54360	0.51310	0.0550*
H6A	0.73040	0.54620	0.36140	0.0490*
H11B	1.136 (3)	0.292 (4)	0.0516 (19)	0.0480*
H12B	0.989 (4)	0.403 (4)	0.115 (3)	0.0480*
H21B	0.99070	0.05190	0.10570	0.0530*
H22B	0.81660	0.17170	0.03950	0.0530*
H31B	0.73940	0.26730	0.23540	0.0580*
H32B	0.72390	0.06300	0.22950	0.0580*
H51B	1.19150	0.28100	0.41940	0.0540*
H52B	1.01740	0.39730	0.35000	0.0540*
H61B	1.29050	0.40160	0.23540	0.0530*
H62B	1.29100	0.19690	0.22820	0.0530*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2A	0.0498 (11)	0.0536 (13)	0.0445 (11)	0.0152 (10)	0.0162 (9)	0.0143 (10)
O11A	0.0413 (10)	0.0609 (14)	0.0647 (13)	0.0137 (10)	0.0181 (9)	−0.0134 (11)
O12A	0.0545 (11)	0.0509 (11)	0.0453 (11)	0.0018 (10)	0.0267 (9)	0.0009 (11)
C1A	0.0314 (12)	0.0299 (14)	0.0366 (14)	−0.0005 (11)	0.0093 (10)	−0.0050 (11)
C2A	0.0375 (12)	0.0311 (13)	0.0331 (13)	0.0013 (12)	0.0090 (10)	−0.0032 (12)
C3A	0.0368 (12)	0.0424 (15)	0.0453 (15)	0.0030 (13)	0.0142 (11)	−0.0051 (14)
C4A	0.0517 (15)	0.0450 (16)	0.0372 (16)	−0.0080 (14)	0.0209 (13)	−0.0040 (13)
C5A	0.0614 (17)	0.0446 (17)	0.0318 (13)	0.0009 (15)	0.0078 (12)	0.0024 (13)
C6A	0.0413 (14)	0.0398 (17)	0.0397 (14)	0.0062 (13)	0.0015 (12)	−0.0039 (13)
C11A	0.0384 (14)	0.0364 (15)	0.0396 (16)	−0.0050 (13)	0.0130 (12)	−0.0134 (12)
O4B	0.0664 (12)	0.0488 (13)	0.0421 (11)	0.0033 (10)	0.0243 (10)	0.0063 (10)
N1B	0.0470 (12)	0.0410 (13)	0.0363 (12)	0.0043 (12)	0.0207 (10)	0.0029 (11)
C2B	0.0428 (14)	0.0496 (18)	0.0417 (15)	−0.0011 (14)	0.0123 (12)	−0.0075 (13)
C3B	0.0440 (14)	0.0501 (19)	0.0561 (18)	−0.0092 (14)	0.0229 (14)	−0.0111 (15)
C5B	0.0480 (14)	0.0514 (17)	0.0377 (15)	0.0064 (16)	0.0091 (11)	−0.0041 (15)
C6B	0.0352 (12)	0.0504 (16)	0.0480 (16)	0.0010 (14)	0.0104 (11)	−0.0048 (14)

Geometric parameters (Å, º)

O2A—C2A	1.358 (3)	C5A—C6A	1.380 (3)
O11A—C11A	1.236 (3)	C3A—H3A	0.9500
O12A—C11A	1.278 (3)	C4A—H4A	0.9500
O2A—H2A	0.88 (2)	C5A—H5A	0.9500
O4B—C3B	1.425 (4)	C6A—H6A	0.9500
O4B—C5B	1.423 (3)	C2B—C3B	1.505 (4)
N1B—C6B	1.486 (3)	C5B—C6B	1.493 (3)
N1B—C2B	1.477 (4)	C2B—H21B	0.9900
N1B—H12B	0.90 (3)	C2B—H22B	0.9900
N1B—H11B	0.93 (2)	C3B—H31B	0.9900
C1A—C6A	1.389 (3)	C3B—H32B	0.9900
C1A—C11A	1.491 (3)	C5B—H51B	0.9900
C1A—C2A	1.404 (3)	C5B—H52B	0.9900
C2A—C3A	1.382 (3)	C6B—H61B	0.9900
C3A—C4A	1.371 (3)	C6B—H62B	0.9900
C4A—C5A	1.368 (4)
C2A—O2A—H2A	106.7 (17)	C1A—C6A—H6A	119.00
C3B—O4B—C5B	110.64 (19)	C5A—C6A—H6A	119.00
C2B—N1B—C6B	111.0 (2)	N1B—C2B—C3B	109.0 (2)
H11B—N1B—H12B	115 (3)	O4B—C3B—C2B	110.5 (2)
C6B—N1B—H12B	110 (2)	O4B—C5B—C6B	111.3 (2)
C2B—N1B—H12B	108.5 (18)	N1B—C6B—C5B	109.55 (18)
C6B—N1B—H11B	104.6 (13)	N1B—C2B—H21B	110.00
C2B—N1B—H11B	107.7 (18)	N1B—C2B—H22B	110.00
C6A—C1A—C11A	120.8 (2)	C3B—C2B—H21B	110.00
C2A—C1A—C11A	121.2 (2)	C3B—C2B—H22B	110.00
C2A—C1A—C6A	118.1 (2)	H21B—C2B—H22B	108.00
O2A—C2A—C3A	118.2 (2)	O4B—C3B—H31B	110.00
O2A—C2A—C1A	121.57 (19)	O4B—C3B—H32B	110.00
C1A—C2A—C3A	120.2 (2)	C2B—C3B—H31B	110.00
C2A—C3A—C4A	120.0 (3)	C2B—C3B—H32B	110.00
C3A—C4A—C5A	121.0 (2)	H31B—C3B—H32B	108.00
C4A—C5A—C6A	119.5 (2)	O4B—C5B—H51B	109.00
C1A—C6A—C5A	121.2 (2)	O4B—C5B—H52B	109.00
O11A—C11A—C1A	119.8 (2)	C6B—C5B—H51B	109.00
O12A—C11A—C1A	116.5 (2)	C6B—C5B—H52B	109.00
O11A—C11A—O12A	123.7 (2)	H51B—C5B—H52B	108.00
C4A—C3A—H3A	120.00	N1B—C6B—H61B	110.00
C2A—C3A—H3A	120.00	N1B—C6B—H62B	110.00
C5A—C4A—H4A	120.00	C5B—C6B—H61B	110.00
C3A—C4A—H4A	120.00	C5B—C6B—H62B	110.00
C6A—C5A—H5A	120.00	H61B—C6B—H62B	108.00
C4A—C5A—H5A	120.00
C5B—O4B—C3B—C2B	61.1 (3)	C11A—C1A—C2A—C3A	177.3 (2)
C3B—O4B—C5B—C6B	−60.4 (3)	C6A—C1A—C2A—O2A	178.7 (2)
C6B—N1B—C2B—C3B	55.6 (3)	C6A—C1A—C2A—C3A	−2.2 (4)
C2B—N1B—C6B—C5B	−54.8 (3)	O2A—C2A—C3A—C4A	−178.8 (2)
C2A—C1A—C6A—C5A	0.8 (4)	C1A—C2A—C3A—C4A	2.0 (4)
C11A—C1A—C6A—C5A	−178.7 (2)	C2A—C3A—C4A—C5A	−0.3 (4)
C2A—C1A—C11A—O11A	−172.2 (2)	C3A—C4A—C5A—C6A	−1.1 (4)
C2A—C1A—C11A—O12A	7.9 (3)	C4A—C5A—C6A—C1A	0.8 (4)
C6A—C1A—C11A—O11A	7.3 (4)	N1B—C2B—C3B—O4B	−58.4 (3)
C6A—C1A—C11A—O12A	−172.6 (2)	O4B—C5B—C6B—N1B	56.6 (3)
C11A—C1A—C2A—O2A	−1.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H2A···O12A	0.88 (2)	1.72 (2)	2.517 (3)	150 (3)
N1B—H11B···O12A^i	0.93 (2)	1.81 (2)	2.715 (3)	164 (2)
N1B—H12B···O11A	0.90 (3)	1.88 (3)	2.765 (3)	167 (3)
C4A—H4A···O4B^ii	0.95	2.42	3.359 (3)	168
C2B—H22B···O2A^iii	0.99	2.57	3.401 (3)	142

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

(II) Tetrahydro-2H-1,4-oxazin-4-ium 2-carboxy-4,6-dinitrophenolate

Crystal data

C4H10NO^+·C7H3N2O7^−	F(000) = 1312
Mr = 315.24	Dx = 1.592 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ya	Cell parameters from 1614 reflections
a = 17.8382 (11) Å	θ = 3.8–28.4°
b = 10.3220 (7) Å	µ = 0.14 mm^−1
c = 14.5599 (11) Å	T = 200 K
β = 101.060 (6)°	Prism, yellow
V = 2631.1 (3) Å^3	0.40 × 0.25 × 0.20 mm
Z = 8

Data collection

Oxford Gemini-S CCD area-detector diffractometer	2574 independent reflections
Radiation source: Enhance(Mo) X-ray source	2054 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.3°
ω scans	h = −21→21
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −12→12
Tmin = 0.941, Tmax = 0.990	l = −17→17
6502 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.098	w = 1/[σ^2(Fo^2) + (0.0396P)^2 + 1.5569P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
2574 reflections	Δρmax = 0.26 e Å^−3
209 parameters	Δρmin = −0.21 e Å^−3
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 2012), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0032 (3)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
O2A	0.69972 (6)	0.48355 (11)	0.14267 (9)	0.0313 (4)
O11A	0.90900 (7)	0.40977 (13)	0.08121 (9)	0.0400 (4)
O12A	0.82689 (7)	0.55446 (12)	0.11366 (10)	0.0415 (4)
O31A	0.56295 (7)	0.37910 (12)	0.15084 (10)	0.0456 (5)
O32A	0.56599 (7)	0.18398 (11)	0.20203 (9)	0.0347 (4)
O51A	0.74856 (8)	−0.11607 (13)	0.13537 (11)	0.0541 (5)
O52A	0.85334 (9)	−0.04831 (14)	0.10034 (12)	0.0637 (6)
N3A	0.59529 (7)	0.27504 (13)	0.16800 (9)	0.0255 (4)
N5A	0.79013 (9)	−0.02916 (15)	0.11825 (10)	0.0350 (5)
C1A	0.79170 (9)	0.33124 (16)	0.11395 (10)	0.0232 (5)
C2A	0.71808 (9)	0.36495 (15)	0.13410 (10)	0.0227 (5)
C3A	0.67071 (8)	0.25631 (15)	0.14567 (10)	0.0219 (5)
C4A	0.69332 (9)	0.12930 (16)	0.14017 (10)	0.0243 (5)
C5A	0.76489 (9)	0.10448 (15)	0.12164 (11)	0.0246 (5)
C6A	0.81337 (9)	0.20394 (16)	0.10787 (10)	0.0253 (5)
C11A	0.84758 (9)	0.43439 (17)	0.10142 (11)	0.0289 (5)
O4B	0.55479 (7)	0.91723 (11)	0.10054 (8)	0.0341 (4)
N1B	0.57210 (9)	0.64544 (15)	0.11609 (13)	0.0411 (6)
C2B	0.57955 (10)	0.71590 (18)	0.02881 (13)	0.0367 (6)
C3B	0.53192 (10)	0.83645 (17)	0.02140 (12)	0.0313 (6)
C5B	0.54399 (11)	0.85268 (19)	0.18286 (12)	0.0364 (6)
C6B	0.59088 (10)	0.7316 (2)	0.19930 (13)	0.0409 (7)
H4A	0.66020	0.06020	0.14900	0.0290*
H6A	0.86210	0.18440	0.09410	0.0300*
H12A	0.7794 (10)	0.549 (2)	0.1269 (15)	0.0620*
H11B	0.5247 (9)	0.6151 (19)	0.1093 (14)	0.0490*
H12B	0.6029 (11)	0.5751 (17)	0.1231 (13)	0.0490*
H21B	0.56210	0.65990	−0.02630	0.0440*
H22B	0.63370	0.73880	0.03050	0.0440*
H31B	0.53710	0.88440	−0.03590	0.0380*
H32B	0.47750	0.81260	0.01630	0.0380*
H51B	0.48930	0.83050	0.17730	0.0440*
H52B	0.55840	0.91140	0.23720	0.0440*
H61B	0.64590	0.75390	0.21080	0.0490*
H62B	0.58020	0.68610	0.25520	0.0490*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O2A	0.0232 (6)	0.0236 (6)	0.0472 (8)	0.0015 (5)	0.0071 (5)	0.0003 (5)
O11A	0.0208 (7)	0.0490 (8)	0.0521 (8)	−0.0011 (6)	0.0118 (6)	0.0094 (6)
O12A	0.0279 (7)	0.0327 (7)	0.0660 (9)	−0.0046 (6)	0.0144 (7)	0.0039 (6)
O31A	0.0294 (7)	0.0336 (7)	0.0789 (10)	0.0109 (6)	0.0234 (7)	0.0152 (7)
O32A	0.0311 (7)	0.0297 (7)	0.0483 (8)	−0.0056 (5)	0.0199 (6)	−0.0014 (6)
O51A	0.0395 (8)	0.0279 (7)	0.0948 (12)	−0.0009 (6)	0.0130 (8)	−0.0017 (7)
O52A	0.0550 (10)	0.0469 (9)	0.1022 (13)	0.0224 (8)	0.0480 (9)	0.0102 (9)
N3A	0.0206 (7)	0.0271 (8)	0.0289 (7)	−0.0001 (6)	0.0051 (6)	0.0001 (6)
N5A	0.0328 (9)	0.0328 (9)	0.0398 (9)	0.0076 (7)	0.0081 (7)	−0.0025 (7)
C1A	0.0176 (8)	0.0311 (9)	0.0198 (8)	−0.0013 (7)	0.0010 (6)	0.0023 (7)
C2A	0.0201 (8)	0.0266 (9)	0.0203 (8)	0.0018 (7)	0.0011 (6)	0.0029 (7)
C3A	0.0174 (8)	0.0257 (9)	0.0225 (8)	0.0013 (6)	0.0037 (6)	0.0013 (6)
C4A	0.0225 (8)	0.0273 (9)	0.0227 (8)	−0.0018 (7)	0.0030 (6)	−0.0002 (7)
C5A	0.0237 (9)	0.0262 (9)	0.0233 (8)	0.0055 (7)	0.0029 (6)	−0.0007 (7)
C6A	0.0190 (8)	0.0358 (10)	0.0211 (8)	0.0033 (7)	0.0041 (6)	0.0007 (7)
C11A	0.0203 (9)	0.0365 (10)	0.0291 (9)	0.0000 (7)	0.0025 (7)	0.0056 (7)
O4B	0.0373 (7)	0.0238 (6)	0.0420 (7)	−0.0031 (5)	0.0095 (6)	−0.0008 (5)
N1B	0.0211 (8)	0.0237 (8)	0.0778 (13)	0.0034 (7)	0.0079 (8)	0.0098 (8)
C2B	0.0295 (10)	0.0380 (10)	0.0437 (11)	0.0011 (8)	0.0096 (8)	−0.0097 (9)
C3B	0.0306 (10)	0.0339 (10)	0.0300 (9)	0.0016 (8)	0.0074 (7)	0.0033 (8)
C5B	0.0320 (10)	0.0464 (11)	0.0310 (10)	−0.0011 (9)	0.0066 (8)	−0.0030 (8)
C6B	0.0276 (10)	0.0541 (13)	0.0401 (11)	0.0000 (9)	0.0039 (8)	0.0170 (9)

Geometric parameters (Å, º)

O2A—C2A	1.2795 (19)	C1A—C11A	1.493 (2)
O11A—C11A	1.215 (2)	C2A—C3A	1.433 (2)
O12A—C11A	1.315 (2)	C3A—C4A	1.379 (2)
O31A—N3A	1.2221 (18)	C4A—C5A	1.379 (2)
O32A—N3A	1.2254 (18)	C5A—C6A	1.382 (2)
O51A—N5A	1.220 (2)	C4A—H4A	0.9500
O52A—N5A	1.221 (2)	C6A—H6A	0.9500
O12A—H12A	0.906 (19)	C2B—C3B	1.499 (3)
O4B—C5B	1.416 (2)	C5B—C6B	1.497 (3)
O4B—C3B	1.417 (2)	C2B—H21B	0.9900
N3A—C3A	1.4563 (19)	C2B—H22B	0.9900
N5A—C5A	1.455 (2)	C3B—H31B	0.9900
N1B—C2B	1.492 (3)	C3B—H32B	0.9900
N1B—C6B	1.488 (3)	C5B—H51B	0.9900
N1B—H11B	0.889 (17)	C5B—H52B	0.9900
N1B—H12B	0.904 (19)	C6B—H61B	0.9900
C1A—C2A	1.442 (2)	C6B—H62B	0.9900
C1A—C6A	1.377 (2)
C11A—O12A—H12A	105.6 (13)	O11A—C11A—C1A	122.32 (16)
C3B—O4B—C5B	110.28 (13)	C5A—C4A—H4A	121.00
O32A—N3A—C3A	118.19 (13)	C3A—C4A—H4A	121.00
O31A—N3A—O32A	122.38 (13)	C1A—C6A—H6A	120.00
O31A—N3A—C3A	119.41 (13)	C5A—C6A—H6A	120.00
O51A—N5A—C5A	119.09 (15)	N1B—C2B—C3B	108.91 (15)
O51A—N5A—O52A	123.17 (16)	O4B—C3B—C2B	111.04 (14)
O52A—N5A—C5A	117.72 (15)	O4B—C5B—C6B	111.43 (15)
C2B—N1B—C6B	111.05 (14)	N1B—C6B—C5B	109.70 (15)
C2B—N1B—H11B	108.4 (13)	N1B—C2B—H21B	110.00
C6B—N1B—H12B	110.5 (12)	N1B—C2B—H22B	110.00
H11B—N1B—H12B	105.9 (17)	C3B—C2B—H21B	110.00
C6B—N1B—H11B	111.2 (13)	C3B—C2B—H22B	110.00
C2B—N1B—H12B	109.6 (12)	H21B—C2B—H22B	108.00
C2A—C1A—C11A	120.53 (14)	O4B—C3B—H31B	109.00
C6A—C1A—C11A	118.05 (15)	O4B—C3B—H32B	109.00
C2A—C1A—C6A	121.40 (15)	C2B—C3B—H31B	109.00
O2A—C2A—C1A	120.72 (14)	C2B—C3B—H32B	109.00
C1A—C2A—C3A	114.55 (14)	H31B—C3B—H32B	108.00
O2A—C2A—C3A	124.71 (14)	O4B—C5B—H51B	109.00
N3A—C3A—C2A	120.87 (13)	O4B—C5B—H52B	109.00
C2A—C3A—C4A	123.48 (14)	C6B—C5B—H51B	109.00
N3A—C3A—C4A	115.62 (13)	C6B—C5B—H52B	109.00
C3A—C4A—C5A	118.71 (15)	H51B—C5B—H52B	108.00
C4A—C5A—C6A	121.29 (15)	N1B—C6B—H61B	110.00
N5A—C5A—C6A	119.56 (15)	N1B—C6B—H62B	110.00
N5A—C5A—C4A	119.15 (14)	C5B—C6B—H61B	110.00
C1A—C6A—C5A	120.56 (15)	C5B—C6B—H62B	110.00
O11A—C11A—O12A	121.31 (16)	H61B—C6B—H62B	108.00
O12A—C11A—C1A	116.37 (14)
C3B—O4B—C5B—C6B	61.04 (19)	C6A—C1A—C11A—O12A	−175.75 (14)
C5B—O4B—C3B—C2B	−62.18 (18)	C11A—C1A—C6A—C5A	178.06 (14)
O31A—N3A—C3A—C4A	−161.19 (14)	C2A—C1A—C11A—O11A	−177.39 (15)
O32A—N3A—C3A—C2A	−160.26 (14)	C2A—C1A—C11A—O12A	2.8 (2)
O31A—N3A—C3A—C2A	21.1 (2)	C6A—C1A—C11A—O11A	4.1 (2)
O32A—N3A—C3A—C4A	17.5 (2)	O2A—C2A—C3A—C4A	−176.97 (15)
O51A—N5A—C5A—C6A	176.16 (15)	C1A—C2A—C3A—N3A	178.86 (13)
O51A—N5A—C5A—C4A	−2.8 (2)	O2A—C2A—C3A—N3A	0.6 (2)
O52A—N5A—C5A—C6A	−2.1 (2)	C1A—C2A—C3A—C4A	1.3 (2)
O52A—N5A—C5A—C4A	178.95 (16)	N3A—C3A—C4A—C5A	−178.37 (13)
C2B—N1B—C6B—C5B	53.25 (19)	C2A—C3A—C4A—C5A	−0.7 (2)
C6B—N1B—C2B—C3B	−54.09 (19)	C3A—C4A—C5A—C6A	−0.6 (2)
C2A—C1A—C6A—C5A	−0.4 (2)	C3A—C4A—C5A—N5A	178.32 (14)
C11A—C1A—C2A—O2A	−0.8 (2)	N5A—C5A—C6A—C1A	−177.76 (14)
C11A—C1A—C2A—C3A	−179.17 (13)	C4A—C5A—C6A—C1A	1.1 (2)
C6A—C1A—C2A—O2A	177.62 (14)	N1B—C2B—C3B—O4B	58.36 (19)
C6A—C1A—C2A—C3A	−0.7 (2)	O4B—C5B—C6B—N1B	−56.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1B—H11B···O11A^i	0.89 (2)	2.04 (2)	2.912 (2)	166 (2)
O12A—H12A···O2A	0.91 (2)	1.63 (2)	2.4956 (17)	159 (2)
N1B—H12B···O2A	0.90 (2)	1.94 (2)	2.790 (2)	156 (2)
N1B—H12B···O31A	0.90 (2)	2.21 (2)	2.806 (2)	123 (2)
C4A—H4A···O4B^ii	0.95	2.39	3.269 (2)	154
C3B—H31B···O52A^iii	0.99	2.43	3.184 (2)	133

Symmetry codes: (i) x−1/2, −y+1, z; (ii) x, y−1, z; (iii) −x+3/2, y+1, −z.

(III) Tetrahydro-2H-1,4-oxazin-4-ium 3,5-dinitrobenzoate

Crystal data

C4H10NO^+·C7H3N2O6^−	F(000) = 1248
Mr = 299.24	Dx = 1.545 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1302 reflections
a = 21.208 (2) Å	θ = 3.8–26.5°
b = 5.6443 (4) Å	µ = 0.13 mm^−1
c = 23.9753 (19) Å	T = 200 K
β = 116.326 (12)°	Prism, colourless
V = 2572.3 (4) Å^3	0.28 × 0.10 × 0.04 mm
Z = 8

Data collection

Oxford Gemini-S CCD area-detector diffractometer	2520 independent reflections
Radiation source: fine-focus sealed tube	1647 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.4°
ω scans	h = −26→14
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −4→6
Tmin = 0.969, Tmax = 0.990	l = −28→29
5493 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0425P)^2] where P = (Fo^2 + 2Fc^2)/3
2520 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 0.25 e Å^−3
2 restraints	Δρmin = −0.21 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
O11A	0.27676 (10)	0.6597 (3)	0.57238 (7)	0.0349 (6)
O12A	0.33171 (11)	0.3191 (3)	0.61217 (7)	0.0381 (7)
O31A	0.49617 (11)	0.2706 (3)	0.82899 (8)	0.0387 (7)
O32A	0.50011 (12)	0.5436 (4)	0.89355 (7)	0.0524 (7)
O51A	0.34011 (11)	1.2034 (3)	0.82039 (8)	0.0368 (7)
O52A	0.26964 (10)	1.2351 (3)	0.72244 (8)	0.0355 (7)
N3A	0.47830 (12)	0.4628 (4)	0.84104 (9)	0.0285 (7)
N5A	0.31711 (12)	1.1363 (3)	0.76634 (9)	0.0250 (7)
C1A	0.34932 (14)	0.6364 (4)	0.68093 (10)	0.0223 (8)
C2A	0.40139 (13)	0.5144 (4)	0.72971 (10)	0.0235 (8)
C3A	0.42595 (13)	0.6019 (4)	0.78926 (10)	0.0218 (8)
C4A	0.40076 (14)	0.8080 (4)	0.80302 (11)	0.0236 (8)
C5A	0.34892 (13)	0.9237 (4)	0.75355 (10)	0.0206 (8)
C6A	0.32341 (14)	0.8457 (4)	0.69288 (10)	0.0236 (8)
C11A	0.31689 (14)	0.5311 (5)	0.61597 (10)	0.0264 (9)
O4B	0.08212 (10)	0.3970 (3)	0.55244 (7)	0.0316 (6)
N1B	0.16741 (12)	0.3875 (4)	0.48864 (9)	0.0255 (7)
C2B	0.15912 (15)	0.1768 (4)	0.52206 (11)	0.0285 (9)
C3B	0.14377 (15)	0.2548 (5)	0.57479 (11)	0.0303 (9)
C5B	0.09223 (15)	0.6061 (4)	0.52387 (11)	0.0298 (9)
C6B	0.10530 (14)	0.5444 (5)	0.46860 (10)	0.0286 (9)
H2A	0.42000	0.37150	0.72220	0.0280*
H4A	0.41830	0.86650	0.84440	0.0280*
H61A	0.28860	0.93410	0.65980	0.0280*
H11B	0.2069 (11)	0.474 (4)	0.5139 (10)	0.0320*
H12B	0.1715 (14)	0.329 (4)	0.4542 (9)	0.0320*
H21B	0.20280	0.08140	0.53850	0.0340*
H22B	0.12010	0.07670	0.49290	0.0340*
H31B	0.13730	0.11380	0.59630	0.0360*
H32B	0.18420	0.34640	0.60530	0.0360*
H51B	0.13290	0.69610	0.55460	0.0360*
H52B	0.05000	0.70800	0.51010	0.0360*
H61B	0.06350	0.46360	0.43660	0.0340*
H62B	0.11350	0.69100	0.45010	0.0340*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11A	0.0370 (13)	0.0391 (11)	0.0183 (9)	−0.0032 (10)	0.0029 (9)	0.0005 (8)
O12A	0.0490 (15)	0.0373 (12)	0.0254 (9)	0.0055 (10)	0.0142 (10)	−0.0078 (8)
O31A	0.0394 (14)	0.0343 (12)	0.0391 (11)	0.0115 (10)	0.0143 (10)	0.0030 (9)
O32A	0.0563 (16)	0.0541 (13)	0.0199 (9)	0.0152 (12)	−0.0074 (10)	−0.0060 (9)
O51A	0.0479 (15)	0.0352 (11)	0.0267 (10)	0.0023 (10)	0.0159 (10)	−0.0082 (8)
O52A	0.0353 (13)	0.0370 (11)	0.0313 (10)	0.0111 (10)	0.0122 (10)	0.0074 (9)
N3A	0.0242 (14)	0.0315 (13)	0.0239 (11)	0.0005 (11)	0.0052 (10)	0.0023 (10)
N5A	0.0267 (14)	0.0251 (12)	0.0259 (11)	−0.0012 (11)	0.0140 (11)	0.0022 (10)
C1A	0.0225 (15)	0.0264 (14)	0.0177 (11)	−0.0049 (12)	0.0087 (12)	−0.0026 (11)
C2A	0.0216 (15)	0.0269 (14)	0.0245 (12)	−0.0005 (12)	0.0124 (12)	−0.0018 (11)
C3A	0.0186 (15)	0.0250 (14)	0.0193 (11)	−0.0011 (12)	0.0062 (11)	0.0024 (10)
C4A	0.0246 (16)	0.0261 (13)	0.0186 (12)	−0.0069 (12)	0.0083 (12)	−0.0042 (11)
C5A	0.0200 (15)	0.0204 (13)	0.0226 (12)	−0.0006 (12)	0.0105 (12)	0.0004 (11)
C6A	0.0238 (16)	0.0268 (14)	0.0206 (12)	−0.0012 (12)	0.0103 (12)	0.0038 (10)
C11A	0.0259 (17)	0.0345 (16)	0.0205 (13)	−0.0040 (14)	0.0119 (13)	−0.0017 (12)
O4B	0.0299 (12)	0.0340 (10)	0.0337 (10)	0.0021 (10)	0.0167 (9)	0.0054 (8)
N1B	0.0283 (14)	0.0284 (12)	0.0169 (10)	−0.0035 (11)	0.0075 (10)	−0.0054 (9)
C2B	0.0294 (17)	0.0261 (14)	0.0275 (13)	0.0014 (13)	0.0104 (13)	0.0001 (11)
C3B	0.0346 (19)	0.0306 (16)	0.0259 (13)	0.0023 (14)	0.0136 (14)	0.0044 (12)
C5B	0.0303 (17)	0.0269 (14)	0.0322 (14)	0.0023 (13)	0.0139 (13)	0.0023 (12)
C6B	0.0289 (17)	0.0290 (15)	0.0216 (12)	0.0002 (13)	0.0054 (12)	0.0014 (11)

Geometric parameters (Å, º)

O11A—C11A	1.247 (3)	C2A—C3A	1.376 (3)
O12A—C11A	1.251 (3)	C3A—C4A	1.380 (4)
O31A—N3A	1.225 (3)	C4A—C5A	1.373 (3)
O32A—N3A	1.221 (3)	C5A—C6A	1.380 (3)
O51A—N5A	1.225 (3)	C2A—H2A	0.9500
O52A—N5A	1.222 (3)	C4A—H4A	0.9500
O4B—C5B	1.428 (3)	C6A—H61A	0.9500
O4B—C3B	1.421 (4)	C2B—C3B	1.504 (4)
N3A—C3A	1.472 (3)	C5B—C6B	1.510 (4)
N5A—C5A	1.474 (3)	C2B—H21B	0.9900
N1B—C2B	1.487 (3)	C2B—H22B	0.9900
N1B—C6B	1.480 (4)	C3B—H31B	0.9900
N1B—H11B	0.93 (2)	C3B—H32B	0.9900
N1B—H12B	0.93 (2)	C5B—H51B	0.9900
C1A—C2A	1.384 (3)	C5B—H52B	0.9900
C1A—C11A	1.517 (3)	C6B—H61B	0.9900
C1A—C6A	1.385 (4)	C6B—H62B	0.9900
C3B—O4B—C5B	109.8 (2)	C1A—C2A—H2A	120.00
O31A—N3A—O32A	124.0 (2)	C5A—C4A—H4A	122.00
O31A—N3A—C3A	118.02 (19)	C3A—C4A—H4A	122.00
O32A—N3A—C3A	118.0 (2)	C1A—C6A—H61A	121.00
O51A—N5A—O52A	124.0 (2)	C5A—C6A—H61A	121.00
O51A—N5A—C5A	117.9 (2)	N1B—C2B—C3B	109.9 (2)
O52A—N5A—C5A	118.08 (19)	O4B—C3B—C2B	110.8 (2)
C2B—N1B—C6B	110.7 (2)	O4B—C5B—C6B	110.8 (2)
C6B—N1B—H12B	110.2 (16)	N1B—C6B—C5B	109.67 (19)
C2B—N1B—H11B	111.0 (14)	N1B—C2B—H21B	110.00
H11B—N1B—H12B	111 (2)	N1B—C2B—H22B	110.00
C6B—N1B—H11B	108.3 (15)	C3B—C2B—H21B	110.00
C2B—N1B—H12B	106.0 (14)	C3B—C2B—H22B	110.00
C2A—C1A—C6A	119.4 (2)	H21B—C2B—H22B	108.00
C6A—C1A—C11A	120.4 (2)	O4B—C3B—H31B	109.00
C2A—C1A—C11A	120.1 (2)	O4B—C3B—H32B	110.00
C1A—C2A—C3A	119.4 (2)	C2B—C3B—H31B	110.00
N3A—C3A—C2A	118.7 (2)	C2B—C3B—H32B	110.00
N3A—C3A—C4A	118.4 (2)	H31B—C3B—H32B	108.00
C2A—C3A—C4A	122.8 (2)	O4B—C5B—H51B	109.00
C3A—C4A—C5A	116.2 (2)	O4B—C5B—H52B	110.00
C4A—C5A—C6A	123.2 (2)	C6B—C5B—H51B	109.00
N5A—C5A—C6A	118.5 (2)	C6B—C5B—H52B	109.00
N5A—C5A—C4A	118.2 (2)	H51B—C5B—H52B	108.00
C1A—C6A—C5A	119.0 (2)	N1B—C6B—H61B	110.00
O11A—C11A—O12A	126.6 (2)	N1B—C6B—H62B	110.00
O12A—C11A—C1A	115.8 (2)	C5B—C6B—H61B	110.00
O11A—C11A—C1A	117.6 (2)	C5B—C6B—H62B	110.00
C3A—C2A—H2A	120.00	H61B—C6B—H62B	108.00
C3B—O4B—C5B—C6B	61.8 (3)	C6A—C1A—C11A—O12A	−163.9 (3)
C5B—O4B—C3B—C2B	−61.8 (3)	C11A—C1A—C6A—C5A	173.2 (3)
O31A—N3A—C3A—C4A	174.2 (3)	C11A—C1A—C2A—C3A	−174.3 (3)
O31A—N3A—C3A—C2A	−2.3 (4)	C2A—C1A—C6A—C5A	−1.8 (4)
O32A—N3A—C3A—C4A	−4.3 (4)	C2A—C1A—C11A—O11A	−171.3 (3)
O32A—N3A—C3A—C2A	179.3 (3)	C1A—C2A—C3A—N3A	176.4 (3)
O51A—N5A—C5A—C6A	179.8 (3)	C1A—C2A—C3A—C4A	0.2 (4)
O51A—N5A—C5A—C4A	2.2 (4)	N3A—C3A—C4A—C5A	−176.1 (3)
O52A—N5A—C5A—C4A	−178.0 (3)	C2A—C3A—C4A—C5A	0.1 (4)
O52A—N5A—C5A—C6A	−0.4 (4)	C3A—C4A—C5A—C6A	−1.3 (4)
C6B—N1B—C2B—C3B	−54.1 (3)	C3A—C4A—C5A—N5A	176.1 (2)
C2B—N1B—C6B—C5B	54.0 (3)	N5A—C5A—C6A—C1A	−175.3 (3)
C6A—C1A—C2A—C3A	0.7 (4)	C4A—C5A—C6A—C1A	2.2 (4)
C2A—C1A—C11A—O12A	11.0 (4)	N1B—C2B—C3B—O4B	58.0 (3)
C6A—C1A—C11A—O11A	13.8 (4)	O4B—C5B—C6B—N1B	−57.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1B—H11B···O11A	0.93 (2)	1.85 (2)	2.764 (3)	170 (2)
N1B—H12B···O12A^i	0.93 (2)	1.77 (2)	2.691 (3)	170 (3)
C4A—H4A···O4B^ii	0.95	2.48	3.358 (3)	153
C5B—H52B···O4B^iii	0.99	2.59	3.320 (4)	130

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x, −y+1, −z+1.

(IV) Tetrahydro-2H-1,4-oxazin-4-ium 2-amino-4-nitrobenzoate

Crystal data

C4H10NO^+·C7H5N2O4^−	F(000) = 568
Mr = 269.26	Dx = 1.434 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1653 reflections
a = 9.1015 (7) Å	θ = 3.9–28.6°
b = 7.1128 (6) Å	µ = 0.12 mm^−1
c = 19.2693 (16) Å	T = 200 K
β = 91.233 (7)°	Prism, orange
V = 1247.15 (18) Å^3	0.50 × 0.25 × 0.23 mm
Z = 4

Data collection

Oxford Gemini-S CCD area-detector diffractometer	2447 independent reflections
Radiation source: Enhance (Mo) X-ray source	2029 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 16.077 pixels mm^-1	θmax = 26.0°, θmin = 3.6°
ω scans	h = −6→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	k = −8→8
Tmin = 0.980, Tmax = 0.990	l = −23→23
5434 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.042P)^2 + 0.2101P] where P = (Fo^2 + 2Fc^2)/3
2447 reflections	(Δ/σ)max < 0.001
184 parameters	Δρmax = 0.19 e Å^−3
4 restraints	Δρmin = −0.17 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 > 2sigma(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
O11A	0.26486 (12)	0.54125 (13)	0.47402 (6)	0.0402 (4)
O12A	0.33383 (12)	0.78803 (14)	0.53793 (6)	0.0424 (4)
O41A	−0.13180 (13)	1.34178 (18)	0.33393 (6)	0.0528 (4)
O42A	−0.24816 (13)	1.09270 (19)	0.30028 (7)	0.0586 (4)
N2A	0.28212 (14)	1.12730 (18)	0.48156 (7)	0.0361 (4)
N4A	−0.14843 (14)	1.1711 (2)	0.33286 (7)	0.0394 (4)
C1A	0.15543 (14)	0.83733 (18)	0.44810 (7)	0.0243 (4)
C2A	0.16941 (14)	1.03559 (18)	0.44813 (6)	0.0234 (4)
C3A	0.06659 (15)	1.14150 (19)	0.40935 (7)	0.0272 (4)
C4A	−0.04274 (14)	1.0524 (2)	0.37231 (7)	0.0288 (4)
C5A	−0.05787 (16)	0.8591 (2)	0.36982 (8)	0.0351 (4)
C6A	0.04246 (15)	0.7544 (2)	0.40864 (8)	0.0324 (4)
C11A	0.25880 (15)	0.71296 (19)	0.48970 (7)	0.0292 (4)
O4B	0.59052 (11)	0.35471 (15)	0.73435 (5)	0.0363 (3)
N1B	0.51248 (14)	0.56485 (18)	0.61404 (6)	0.0326 (4)
C2B	0.57855 (17)	0.6577 (2)	0.67626 (8)	0.0356 (5)
C3B	0.67228 (17)	0.5166 (2)	0.71577 (8)	0.0390 (5)
C5B	0.52881 (17)	0.2626 (2)	0.67489 (8)	0.0349 (5)
C6B	0.42907 (17)	0.3943 (2)	0.63420 (8)	0.0368 (5)
H3A	0.07300	1.27480	0.40880	0.0330*
H5A	−0.13350	0.80080	0.34280	0.0420*
H6A	0.03410	0.62120	0.40840	0.0390*
H21A	0.2712 (18)	1.251 (2)	0.4860 (9)	0.0430*
H22A	0.3341 (17)	1.058 (2)	0.5128 (8)	0.0430*
H11B	0.4521 (17)	0.646 (2)	0.5898 (8)	0.0390*
H12B	0.5870 (16)	0.531 (2)	0.5839 (8)	0.0390*
H21B	0.50000	0.70550	0.70630	0.0430*
H22B	0.63970	0.76550	0.66200	0.0430*
H31B	0.75560	0.47820	0.68680	0.0470*
H32B	0.71320	0.57650	0.75830	0.0470*
H51B	0.47210	0.15140	0.68980	0.0420*
H52B	0.60870	0.21840	0.64490	0.0420*
H61B	0.39040	0.32990	0.59210	0.0440*
H62B	0.34470	0.43090	0.66290	0.0440*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11A	0.0527 (7)	0.0190 (5)	0.0493 (7)	0.0079 (5)	0.0081 (5)	0.0033 (5)
O12A	0.0476 (6)	0.0301 (6)	0.0488 (7)	0.0072 (5)	−0.0156 (5)	0.0054 (5)
O41A	0.0584 (8)	0.0450 (7)	0.0546 (8)	0.0225 (6)	−0.0084 (6)	0.0065 (6)
O42A	0.0397 (6)	0.0784 (9)	0.0567 (8)	0.0114 (6)	−0.0191 (6)	−0.0059 (7)
N2A	0.0418 (7)	0.0208 (6)	0.0449 (8)	−0.0013 (6)	−0.0141 (6)	0.0023 (6)
N4A	0.0341 (7)	0.0515 (9)	0.0326 (7)	0.0141 (6)	−0.0005 (6)	−0.0011 (6)
C1A	0.0262 (6)	0.0207 (7)	0.0264 (7)	0.0018 (5)	0.0070 (5)	0.0005 (5)
C2A	0.0261 (6)	0.0214 (7)	0.0228 (6)	0.0015 (5)	0.0042 (5)	−0.0002 (5)
C3A	0.0333 (7)	0.0210 (7)	0.0273 (7)	0.0041 (6)	0.0036 (6)	0.0019 (6)
C4A	0.0255 (7)	0.0350 (8)	0.0261 (7)	0.0070 (6)	0.0030 (5)	0.0026 (6)
C5A	0.0287 (7)	0.0377 (8)	0.0389 (8)	−0.0042 (6)	−0.0016 (6)	−0.0049 (7)
C6A	0.0334 (7)	0.0223 (7)	0.0418 (8)	−0.0037 (6)	0.0048 (6)	−0.0020 (6)
C11A	0.0313 (7)	0.0235 (7)	0.0331 (8)	0.0046 (6)	0.0080 (6)	0.0059 (6)
O4B	0.0391 (6)	0.0395 (6)	0.0301 (5)	0.0013 (5)	−0.0041 (4)	0.0049 (5)
N1B	0.0366 (7)	0.0291 (7)	0.0320 (7)	0.0092 (6)	−0.0038 (5)	0.0031 (6)
C2B	0.0388 (8)	0.0284 (8)	0.0394 (8)	−0.0019 (7)	−0.0008 (7)	−0.0028 (7)
C3B	0.0328 (8)	0.0440 (9)	0.0397 (8)	−0.0043 (7)	−0.0070 (7)	−0.0005 (7)
C5B	0.0408 (8)	0.0284 (8)	0.0355 (8)	0.0012 (7)	0.0010 (7)	0.0008 (7)
C6B	0.0364 (8)	0.0338 (8)	0.0396 (8)	−0.0023 (7)	−0.0093 (7)	−0.0020 (7)

Geometric parameters (Å, º)

O11A—C11A	1.2597 (16)	C2A—C3A	1.4041 (18)
O12A—C11A	1.2601 (18)	C3A—C4A	1.3677 (19)
O41A—N4A	1.2235 (19)	C4A—C5A	1.383 (2)
O42A—N4A	1.2266 (18)	C5A—C6A	1.385 (2)
O4B—C5B	1.4247 (18)	C3A—H3A	0.9500
O4B—C3B	1.4210 (18)	C5A—H5A	0.9500
N2A—C2A	1.3654 (18)	C6A—H6A	0.9500
N4A—C4A	1.4780 (19)	C2B—C3B	1.512 (2)
N2A—H22A	0.904 (15)	C5B—C6B	1.512 (2)
N2A—H21A	0.890 (14)	C2B—H21B	0.9900
N1B—C6B	1.4871 (19)	C2B—H22B	0.9900
N1B—C2B	1.4847 (19)	C3B—H31B	0.9900
N1B—H11B	0.918 (15)	C3B—H32B	0.9900
N1B—H12B	0.934 (15)	C5B—H51B	0.9900
C1A—C11A	1.5092 (19)	C5B—H52B	0.9900
C1A—C2A	1.4159 (18)	C6B—H61B	0.9900
C1A—C6A	1.3963 (19)	C6B—H62B	0.9900
C3B—O4B—C5B	111.69 (11)	C2A—C3A—H3A	120.00
O41A—N4A—O42A	123.34 (14)	C6A—C5A—H5A	122.00
O41A—N4A—C4A	118.63 (12)	C4A—C5A—H5A	122.00
O42A—N4A—C4A	118.02 (13)	C1A—C6A—H6A	119.00
C2A—N2A—H21A	115.7 (11)	C5A—C6A—H6A	119.00
C2A—N2A—H22A	115.5 (9)	N1B—C2B—C3B	109.01 (12)
H21A—N2A—H22A	122.2 (14)	O4B—C3B—C2B	111.83 (12)
C2B—N1B—C6B	110.62 (11)	O4B—C5B—C6B	110.74 (12)
H11B—N1B—H12B	106.3 (13)	N1B—C6B—C5B	109.68 (12)
C2B—N1B—H12B	109.3 (9)	N1B—C2B—H21B	110.00
C6B—N1B—H11B	110.0 (9)	N1B—C2B—H22B	110.00
C6B—N1B—H12B	109.5 (9)	C3B—C2B—H21B	110.00
C2B—N1B—H11B	111.0 (9)	C3B—C2B—H22B	110.00
C2A—C1A—C6A	119.08 (12)	H21B—C2B—H22B	108.00
C6A—C1A—C11A	119.01 (12)	O4B—C3B—H31B	109.00
C2A—C1A—C11A	121.91 (11)	O4B—C3B—H32B	109.00
N2A—C2A—C1A	122.86 (12)	C2B—C3B—H31B	109.00
N2A—C2A—C3A	118.69 (12)	C2B—C3B—H32B	109.00
C1A—C2A—C3A	118.38 (12)	H31B—C3B—H32B	108.00
C2A—C3A—C4A	119.88 (12)	O4B—C5B—H51B	109.00
N4A—C4A—C3A	117.51 (13)	O4B—C5B—H52B	109.00
C3A—C4A—C5A	123.35 (13)	C6B—C5B—H51B	110.00
N4A—C4A—C5A	119.14 (12)	C6B—C5B—H52B	110.00
C4A—C5A—C6A	116.87 (13)	H51B—C5B—H52B	108.00
C1A—C6A—C5A	122.42 (13)	N1B—C6B—H61B	110.00
O11A—C11A—C1A	118.09 (12)	N1B—C6B—H62B	110.00
O12A—C11A—C1A	117.72 (12)	C5B—C6B—H61B	110.00
O11A—C11A—O12A	124.19 (13)	C5B—C6B—H62B	110.00
C4A—C3A—H3A	120.00	H61B—C6B—H62B	108.00
C3B—O4B—C5B—C6B	−58.68 (15)	C11A—C1A—C2A—N2A	4.6 (2)
C5B—O4B—C3B—C2B	58.91 (15)	C11A—C1A—C2A—C3A	−178.49 (12)
O41A—N4A—C4A—C5A	−178.10 (13)	C2A—C1A—C6A—C5A	−0.6 (2)
O42A—N4A—C4A—C3A	−178.96 (13)	C11A—C1A—C6A—C5A	179.16 (13)
O41A—N4A—C4A—C3A	1.47 (19)	N2A—C2A—C3A—C4A	176.46 (13)
O42A—N4A—C4A—C5A	1.5 (2)	C1A—C2A—C3A—C4A	−0.59 (19)
C6B—N1B—C2B—C3B	55.45 (15)	C2A—C3A—C4A—N4A	179.58 (12)
C2B—N1B—C6B—C5B	−56.22 (15)	C2A—C3A—C4A—C5A	−0.9 (2)
C6A—C1A—C2A—N2A	−175.63 (13)	C3A—C4A—C5A—C6A	1.5 (2)
C6A—C1A—C2A—C3A	1.29 (19)	N4A—C4A—C5A—C6A	−178.93 (13)
C2A—C1A—C11A—O11A	−162.06 (13)	C4A—C5A—C6A—C1A	−0.8 (2)
C2A—C1A—C11A—O12A	17.82 (19)	N1B—C2B—C3B—O4B	−56.59 (16)
C6A—C1A—C11A—O11A	18.17 (19)	O4B—C5B—C6B—N1B	57.06 (15)
C6A—C1A—C11A—O12A	−161.96 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1B—H11B···O12A	0.92 (2)	1.77 (2)	2.6855 (17)	175 (2)
N1B—H12B···O11A^i	0.93 (2)	1.84 (2)	2.7756 (17)	179 (1)
N2A—H21A···O11A^ii	0.89 (1)	2.08 (1)	2.9519 (16)	167 (2)
N2A—H22A···O12A	0.90 (2)	1.98 (1)	2.6838 (17)	134 (1)
C6B—H62B···O41A^iii	0.99	2.53	3.361 (2)	142

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