Salt forms of the pharmaceutical amide di­hydro­carbamazepine

Carbamazepine (CBZ) is well known as a model active pharmaceutical ingre­dient used in the study of polymorphism and the generation and com­parison of cocrystal forms. The pharmaceutical amide di­hydro­carbamazepine (DCBZ) is a less well known material and is largely of inter­est here as a structural congener of CBZ. Reaction of DCBZ with strong acids results in protonation of the amide functionality at the O atom and gives the salt forms di­hydro­carbamazepine hydro­chloride {systematic name: [(10,11-di­hydro-5H-dibenzo[b,f]azepin-5-yl)(hy­droxy)methyl­idene]aza­nium chloride, C₁₅H₁₅N₂O⁺·Cl^-}, di­hydro­car­bam­azepine hydro­chloride monohydrate {systematic name: [(10,11-di­hydro-5H-dibenzo[b,f]azepin-5-yl)(hy­droxy)methyl­idene]aza­nium chloride monohydrate, C₁₅H₁₅N₂O⁺·Cl^-·H₂O} and di­hydro­carbamazepine hydro­bromide monohydrate {systematic name: [(10,11-di­hydro-5H-dibenzo[b,f]azepin-5-yl)(hy­droxy)methyl­idene]aza­nium bromide monohydrate, C₁₅H₁₅N₂O⁺·Br^-·H₂O}. The anhydrous hydro­chloride has a structure with two crystallographically independent ion pairs (Z' = 2), wherein both cations adopt syn conformations, whilst the two hydrated species are mutually isostructural and have cations with anti conformations. Compared to neutral di­hydro­carbamazepine structures, proton­ation of the amide group is shown to cause changes to both the mol­ecular (C=O bond lengthening and C-N bond shortening) and the supra­molecular structures. The amide-to-amide and dimeric hydrogen-bonding motifs seen for neutral polymorphs and cocrystalline species are replaced here by one-dimensional polymeric constructs with no direct amide-to-amide bonds. The structures are also compared with, and shown to be closely related to, those of the salt forms of the structurally similar pharmaceutical carbamazepine.

S1. Introduction

Carbamazepine (CBZ) is an anti-epilectic drug that is well known to the crystallographic community as a model active pharmaceutical ingredient (API) that has been widely used in the study of polymorphism and the generation and comparison of cocrystal forms (e.g. Gelbrich & Hursthouse, 2006; Fleischman et al., 2003). Recently, it has been shown that despite the relatively nonbasic nature of amides, it is possible to protonate the O atom of the amide group of CBZ using strong acids, thus generating salt forms (Perumalla & Sun, 2012; Eberlin et al., 2013; Buist et al., 2013, 2015). Comparison of the structures of neutral CBZ species with those of cationic CBZ(H) species show that protonation is accompanied both by changes to the molecular structure (lengthening of the C═O bond and shortening of the C—N bonds) and by changes to the packing structure [e.g. the typical R₂²(8) homodimer found in CBZ structures does not occur in the salt forms). Low pH conditions have also been shown to allow easy access to ionic cocrystalline (ICC) forms of CBZ, including hydro­nium, ammonium and Na^I species (Buist et al., 2013, 2015; Buist & Kennedy, 2014). Di­hydro­carbamazepine (DCBZ) is a less well known material and is largely of inter­est here as a structural congener of CBZ. The structures of four polymorphs of DCBZ have been described (Bandoli et al., 1992; Harrison et al., 2006; Leech et al., 2007; Arlin et al., 2010), as have the structures of five cocrystalline or solvate forms (Cruz Cabeza et al., 2006; Johnston et al., 2007, 2007a,b; Oliveira et al., 2011). A single salt form of DCBZ, viz. the methyl sulfonate, has also been reported (Eberlin et al., 2013). The two compounds, CBZ and DCBZ, have broadly similar sizes and shapes and the same single polar functional group. Despite this similarity, it has been noted that their packing behaviours differ. Discussion of these differences has centred about the tendency of CBZ to form R₂²(8) hydrogen-bonded homodimers rather than catemeric chains, whilst the opposite is true of DCBZ (Arlin et al., 2010). Herein we report three salt forms of DCBZ, namely, di­hydro­carbamazepine hydro­chloride, (I), di­hydro­carbamazepine hydro­chloride monohydrate, (II), and di­hydro­carbamazepine hydro­bromide monohydrate, (III), and thus extend the previous work comparing neutral CBZ and DCBZ structures to a comparison of cationic CBZ(H) and DCBZ(H).

S2. Experimental

S2.1. Synthesis and crystallization

S2.1.1. Synthesis of hydro­chloride salts of DCBZ

DCBZ (0.208 g, 0.87 mmol) and NaI (0.0656 g, 0.44 mmol) were dissolved in warm methanol (4 ml). Once the solution had cooled to room temperature, acetyl chloride (1 ml) was added slowly. The reaction vial was covered with a perforated parafilm seal. Crystals of [DCBZ(H)]Cl were deposited within 48 h. Some of the crystals with their mother liquor were then left in the unsealed vial. After 5 d, the solid present was found to be [DCBZ(H)]Cl·H₂O.

S2.1.2. Synthesis of [DCBZ(H)]Br\·H~2Õ

DCBZ (0.198 g, 0.83 mmol) was dissolved in methanol (4 ml). The solution was heated in a water bath until the DCBZ had dissolved. Once the solution had cooled to room temperature, concentrated hydro­bromic acid (1 ml) was added slowly. The reaction test tube was sealed with parafilm. Small holes were made in the parafilm to aid evaporation. Crystals formed over a period of 10 d. The same product was also isolated on reacting a methanol solution of DCBZ with acetyl bromide in the presence of ammonium bromide. Ammonium bromide (here) and NaI (above) were included in attempts to form ionic cocrystalline forms of DCBZ as described for CBZ by Buist & Kennedy (2014).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. For both structures, H atoms bound to C atoms were placed in the expected geometric positions and treated in riding modes, with C—H = 0.95 and 0.99 Å for sp² CH and CH₂ groups, respectively, and with U_iso(H) = 1.2U_eq(C). In (I) and (II), all H atoms bound to N or O atoms were located by difference synthesis and refined isotropically. H atoms bound to N or O atoms in (III) were located and treated similarly, with the exception that it was neccessary to restrain the N—H and O—H distances of the NH₂ and OH₂ groups to 0.88 (2) Å.

S3. Results and discussion

HCl was generated in situ by adding acetyl chloride to a methanol solution of DCBZ. The initial product was anhydrous [DCBZ(H)]Cl (I), (Fig. 1). Leaving crystalline (I) in the mother liquor allowed a transformation to occur and after 5 d, crystals of hydrated form [DCBZ(H)]Cl·H₂O, (II), were recovered (Fig. 2). A similar hydration on exposure to atmospheric moisture is known to cause the transformation of [CBZ(H)]Br to [CBZ(H)]Br·H₂O (Buist et al., 2013). In contrast [CBZ(H)]Cl inter­acts in a more complex fashion with atmospheric moisture, simultaneously losing HCl and absorbing water to give the ICC hydro­nium compound CBZ₂[H₃O]Cl (Buist et al., 2013). Reactions of DCBZ with HBr, whether through a similar in situ generation of acid as described above or simply through use of aqueous HBr, gave only the hydrate [DCBZ(H)]Br·H₂O, (III) (Fig. 3). Examination of the unit-cell dimensions and the structures of (II) and (III) show that they are isostructural. Isostructurality is relatively common for Cl and Br salts of API materials and other examples of isostructurality are found amongst the multiple known phases of Cl and Br salt forms of CBZ (Buist et al., 2013, 2015). Inter­estingly, [DCBZ(H)]Cl, (I), is isostructural with one of the known forms of [CBZ(H)]Br but not with any hydro­chloride phase of CBZ (Buist et al., 2013). The double change in chemical identity with no structural change invites speculation that there could be similar, currently unknown, phases of [CBZ(H)]Cl and [DCBZ(H)]Br that also have the same structure as (I).

There are two crystallographically independent ion pairs in (I), Z' = 2, and the acidic H atom of each cation was clearly located and refined as being bonded to the amide O atom. The molecular geometries of the two cations are essentially similar, with the largest differences involving the position of the C═O group of the amide [cf. 5.9 (3) and 4.3 (3)° for C1—N1—C15—O1 and C20—N3—C30—O2]. Both DCBZ(H) cations in (I) adopt the syn conformation where the C—O vector is parallel to the CH₂—CH₂ vector. For neutral DCBZ, this syn conformation has been shown to be slightly energetically disfavoured (by < 2 kJ mol^-1) when compared to the alternative anti conformation, where the C—NH₂ vector is parallel to the CH₂—CH₂ vector (Arlin et al., 2010). The higher energy syn conformation is also less commonly seen in the crystalline state (Table 2). The DCBZ(H) cations of hydrated structures (II) and (III) both have anti conformations and their acidic protons were again freely refined and located as being bonded to the amide O atoms. As shown in Table 2, protonation of the amide has a significant effect on the C═O and C—N bond lengths, with the former lengthening and the latter shortening. Comparing all four known DCBZ(H) structures with the known neutral DCBZ structures it can be seen that the C═O bonds are 0.05 to 0.09 Å longer for the protonated DCBZ ions, whereas the C—NH₂ and C—N_ring bonds shorten by 0.01–0.04 and 0.03–0.06 Å, respectively. The larger change for C—N_ring as compared to C—NH₂ suggests a significant role for resonance form C (see Scheme 2). Similar bond-length changes are seen on comparing CBZ with CBZ(H). Averaging 47 well-modelled CBZ structures from the Cambridge Structural database (CSD, Version ???; Groom & Allen, 2014) gives values of 1.242, 1.342 and 1.373 Å for the C═O, C—NH₂ and C—N_ring bonds in neutral CBZ species, whereas the equivalent ranges for the known fully protonated CBZ(H) structures are 1.285–1.312, 1.304–1.326 and 1.323–1.348 Å (Eberlin et al., 2013; Buist et al., 2015). For CBZ, these bond-length differences are so well established that species with C═O and C—N bond lengths inter­mediate to the two groups given have convincingly been shown to have structures inter­mediate between salt and cocrystalline forms (Eberlin et al., 2013). Such dynamic equilibria where protons move between two sites are well known (e.g. Cruickshank et al., 2013; Wilson et al., 2006), but have extra significance for ionizable APIs due to the potential for classification/regulation issues. For instance, the FDA Guidance for Industry on the Regulatory Classification of Pharmaceutical Co-Crystals does not consider materials that are in such inter­mediate states between salt and cocrystalline forms (Eberlin et al., 2013). One such inter­mediate species is [CBZ(H)]Br·H₂O, where the acidic H arom is shared by the CBZ and water molecules (Buist et al., 2013). Despite being directly analogous in composition to this hydrated species, neither (II) nor (III) show any sign of having bond lengths that indicate inter­mediate salt–cocrystal character. Note that the two forms of cocrystalline DCBZ in Table 2 that have acid coformers do have the longest C═O bonds and shortest N—C bonds of any of the given neutral species, but these differences are very small compared to those found for the CBZ(H) cations.

Arlin et al. (2010) compare and contrast the hydrogen-bonding motifs found in the polymorphic forms of CBZ and DCBZ. The CBZ structures are dominated by an R₂²(8) homodimer formed by bonding between two amide units. This motif is only seen for one of the four known phases of DCBZ, with the others instead having catenated chain amide-to-amide structures. This structural difference is not repeated for cocrystal and solvate forms of CBZ and DCBZ. CBZ is well studied and two hydrogen-bonded motifs are known to be common. The first is an extension of the R₂²(8) homodimer where the coformer molecules hydrogen bond to the edges of the core CBZ dimeric group. The second is a heterodimer, again R₂²(8), where a COOH-bearing coformer replaces one of the amide units (Gelbrich & Hursthouse, 2006; Fleischman et al., 2003). The known DCBZ cocrystals also display these two motifs with solvated homodimers present in the di­methyl sulfoxide (DMSO) and saccharine species (Johnston et al., 2007b; Oliveira et al., 2011) and the heterodimer present in the acetic acid, formic acid and foramide structures (Cruz Cabeza et al., 2006; Johnston et al., 2007, 2007a). The homodimer motif is not, however, seen in protonated CBZ(H) species as the new OH group makes this unfavourable (Buist et al., 2013, 2015). Equivalents of the heterodimer motif are seen for CBZ(H) with some sulfonate counter-ions, albeit with the proton bound to the O atom of the amide rather than remaining on an acidic coformer (Buist et al., 2015; Eberlin et al., 2013). None of the new DCBZ(H) species structures described herein adopt any of these well known R₂²(8) hydrogen-bonding motifs and so structures of DCBZ(H) can be differentiated from those of DCBZ both by differences in molecular structure (above) and by differences in packing structure. Both (II) and (III) are found to have structures based about cation/anion [DCBZ(H)]₂X₂ dimers that have the R₂⁴(8) graph set. The water molecules inter­act with both cation and anion to give a further ring motif, R₂³(8) (Fig. 4). The [DCBZ(H)]₂X₂ dimers connect through the hydrogen bonds between halide ions and water molecules to give one-dimensional constructs parallel to the crystallographic a direction (Fig. 5). The largest difference in unit-cell length between (II) and (III) is for the a axes and is thus associated with small differences in spacing for this hydrogen-bonded motif. In contrast, the only strong hydrogen-bond acceptors in the structure of (I) are the chloride anions. These each accept hydrogen bonds from an O—H group and from two N—H groups (Table 3). One O—H and one N—H donor per chloride ion are from a single DCBZ(H) cation (giving an R₁²(6) motif), but the second N—H donor is from an independent cation and thus the hydrogen bonding propagates to give one-dimensional motifs parallel to the crystallographic a axis (Fig. 6). As (I) is isostructural with Form 1 of [CBZ(H)]Br, this is obviously a hydrogen-bonding system that is common to both the DCBZ(H) and CBZ(H) species. The hydrogen-bonding structure in (II) and (III) (Table 4 and 5) also has precedence in CBZ(H) chemistry, as similar supra­molecular structures are present in both [CBZ(H)]Cl·H₂O and [CBZ(H)]Br·H₂O (Buist et al., 2013, 2015). Thus, although the polymorphic forms of CBZ display different supra­molecular chemistry from the polymorphic forms of DCBZ, the salt forms (as with the cocrystalline forms) of the two APIs have stuctures based around the same inter­molecular hydrogen bonding.

Structure description

Carbamazepine (CBZ) is an anti-epilectic drug that is well known to the crystallographic community as a model active pharmaceutical ingredient (API) that has been widely used in the study of polymorphism and the generation and comparison of cocrystal forms (e.g. Gelbrich & Hursthouse, 2006; Fleischman et al., 2003). Recently, it has been shown that despite the relatively nonbasic nature of amides, it is possible to protonate the O atom of the amide group of CBZ using strong acids, thus generating salt forms (Perumalla & Sun, 2012; Eberlin et al., 2013; Buist et al., 2013, 2015). Comparison of the structures of neutral CBZ species with those of cationic CBZ(H) species show that protonation is accompanied both by changes to the molecular structure (lengthening of the C═O bond and shortening of the C—N bonds) and by changes to the packing structure [e.g. the typical R₂²(8) homodimer found in CBZ structures does not occur in the salt forms). Low pH conditions have also been shown to allow easy access to ionic cocrystalline (ICC) forms of CBZ, including hydro­nium, ammonium and Na^I species (Buist et al., 2013, 2015; Buist & Kennedy, 2014). Di­hydro­carbamazepine (DCBZ) is a less well known material and is largely of inter­est here as a structural congener of CBZ. The structures of four polymorphs of DCBZ have been described (Bandoli et al., 1992; Harrison et al., 2006; Leech et al., 2007; Arlin et al., 2010), as have the structures of five cocrystalline or solvate forms (Cruz Cabeza et al., 2006; Johnston et al., 2007, 2007a,b; Oliveira et al., 2011). A single salt form of DCBZ, viz. the methyl sulfonate, has also been reported (Eberlin et al., 2013). The two compounds, CBZ and DCBZ, have broadly similar sizes and shapes and the same single polar functional group. Despite this similarity, it has been noted that their packing behaviours differ. Discussion of these differences has centred about the tendency of CBZ to form R₂²(8) hydrogen-bonded homodimers rather than catemeric chains, whilst the opposite is true of DCBZ (Arlin et al., 2010). Herein we report three salt forms of DCBZ, namely, di­hydro­carbamazepine hydro­chloride, (I), di­hydro­carbamazepine hydro­chloride monohydrate, (II), and di­hydro­carbamazepine hydro­bromide monohydrate, (III), and thus extend the previous work comparing neutral CBZ and DCBZ structures to a comparison of cationic CBZ(H) and DCBZ(H).

HCl was generated in situ by adding acetyl chloride to a methanol solution of DCBZ. The initial product was anhydrous [DCBZ(H)]Cl (I), (Fig. 1). Leaving crystalline (I) in the mother liquor allowed a transformation to occur and after 5 d, crystals of hydrated form [DCBZ(H)]Cl·H₂O, (II), were recovered (Fig. 2). A similar hydration on exposure to atmospheric moisture is known to cause the transformation of [CBZ(H)]Br to [CBZ(H)]Br·H₂O (Buist et al., 2013). In contrast [CBZ(H)]Cl inter­acts in a more complex fashion with atmospheric moisture, simultaneously losing HCl and absorbing water to give the ICC hydro­nium compound CBZ₂[H₃O]Cl (Buist et al., 2013). Reactions of DCBZ with HBr, whether through a similar in situ generation of acid as described above or simply through use of aqueous HBr, gave only the hydrate [DCBZ(H)]Br·H₂O, (III) (Fig. 3). Examination of the unit-cell dimensions and the structures of (II) and (III) show that they are isostructural. Isostructurality is relatively common for Cl and Br salts of API materials and other examples of isostructurality are found amongst the multiple known phases of Cl and Br salt forms of CBZ (Buist et al., 2013, 2015). Inter­estingly, [DCBZ(H)]Cl, (I), is isostructural with one of the known forms of [CBZ(H)]Br but not with any hydro­chloride phase of CBZ (Buist et al., 2013). The double change in chemical identity with no structural change invites speculation that there could be similar, currently unknown, phases of [CBZ(H)]Cl and [DCBZ(H)]Br that also have the same structure as (I).

There are two crystallographically independent ion pairs in (I), Z' = 2, and the acidic H atom of each cation was clearly located and refined as being bonded to the amide O atom. The molecular geometries of the two cations are essentially similar, with the largest differences involving the position of the C═O group of the amide [cf. 5.9 (3) and 4.3 (3)° for C1—N1—C15—O1 and C20—N3—C30—O2]. Both DCBZ(H) cations in (I) adopt the syn conformation where the C—O vector is parallel to the CH₂—CH₂ vector. For neutral DCBZ, this syn conformation has been shown to be slightly energetically disfavoured (by < 2 kJ mol^-1) when compared to the alternative anti conformation, where the C—NH₂ vector is parallel to the CH₂—CH₂ vector (Arlin et al., 2010). The higher energy syn conformation is also less commonly seen in the crystalline state (Table 2). The DCBZ(H) cations of hydrated structures (II) and (III) both have anti conformations and their acidic protons were again freely refined and located as being bonded to the amide O atoms. As shown in Table 2, protonation of the amide has a significant effect on the C═O and C—N bond lengths, with the former lengthening and the latter shortening. Comparing all four known DCBZ(H) structures with the known neutral DCBZ structures it can be seen that the C═O bonds are 0.05 to 0.09 Å longer for the protonated DCBZ ions, whereas the C—NH₂ and C—N_ring bonds shorten by 0.01–0.04 and 0.03–0.06 Å, respectively. The larger change for C—N_ring as compared to C—NH₂ suggests a significant role for resonance form C (see Scheme 2). Similar bond-length changes are seen on comparing CBZ with CBZ(H). Averaging 47 well-modelled CBZ structures from the Cambridge Structural database (CSD, Version ???; Groom & Allen, 2014) gives values of 1.242, 1.342 and 1.373 Å for the C═O, C—NH₂ and C—N_ring bonds in neutral CBZ species, whereas the equivalent ranges for the known fully protonated CBZ(H) structures are 1.285–1.312, 1.304–1.326 and 1.323–1.348 Å (Eberlin et al., 2013; Buist et al., 2015). For CBZ, these bond-length differences are so well established that species with C═O and C—N bond lengths inter­mediate to the two groups given have convincingly been shown to have structures inter­mediate between salt and cocrystalline forms (Eberlin et al., 2013). Such dynamic equilibria where protons move between two sites are well known (e.g. Cruickshank et al., 2013; Wilson et al., 2006), but have extra significance for ionizable APIs due to the potential for classification/regulation issues. For instance, the FDA Guidance for Industry on the Regulatory Classification of Pharmaceutical Co-Crystals does not consider materials that are in such inter­mediate states between salt and cocrystalline forms (Eberlin et al., 2013). One such inter­mediate species is [CBZ(H)]Br·H₂O, where the acidic H arom is shared by the CBZ and water molecules (Buist et al., 2013). Despite being directly analogous in composition to this hydrated species, neither (II) nor (III) show any sign of having bond lengths that indicate inter­mediate salt–cocrystal character. Note that the two forms of cocrystalline DCBZ in Table 2 that have acid coformers do have the longest C═O bonds and shortest N—C bonds of any of the given neutral species, but these differences are very small compared to those found for the CBZ(H) cations.

Arlin et al. (2010) compare and contrast the hydrogen-bonding motifs found in the polymorphic forms of CBZ and DCBZ. The CBZ structures are dominated by an R₂²(8) homodimer formed by bonding between two amide units. This motif is only seen for one of the four known phases of DCBZ, with the others instead having catenated chain amide-to-amide structures. This structural difference is not repeated for cocrystal and solvate forms of CBZ and DCBZ. CBZ is well studied and two hydrogen-bonded motifs are known to be common. The first is an extension of the R₂²(8) homodimer where the coformer molecules hydrogen bond to the edges of the core CBZ dimeric group. The second is a heterodimer, again R₂²(8), where a COOH-bearing coformer replaces one of the amide units (Gelbrich & Hursthouse, 2006; Fleischman et al., 2003). The known DCBZ cocrystals also display these two motifs with solvated homodimers present in the di­methyl sulfoxide (DMSO) and saccharine species (Johnston et al., 2007b; Oliveira et al., 2011) and the heterodimer present in the acetic acid, formic acid and foramide structures (Cruz Cabeza et al., 2006; Johnston et al., 2007, 2007a). The homodimer motif is not, however, seen in protonated CBZ(H) species as the new OH group makes this unfavourable (Buist et al., 2013, 2015). Equivalents of the heterodimer motif are seen for CBZ(H) with some sulfonate counter-ions, albeit with the proton bound to the O atom of the amide rather than remaining on an acidic coformer (Buist et al., 2015; Eberlin et al., 2013). None of the new DCBZ(H) species structures described herein adopt any of these well known R₂²(8) hydrogen-bonding motifs and so structures of DCBZ(H) can be differentiated from those of DCBZ both by differences in molecular structure (above) and by differences in packing structure. Both (II) and (III) are found to have structures based about cation/anion [DCBZ(H)]₂X₂ dimers that have the R₂⁴(8) graph set. The water molecules inter­act with both cation and anion to give a further ring motif, R₂³(8) (Fig. 4). The [DCBZ(H)]₂X₂ dimers connect through the hydrogen bonds between halide ions and water molecules to give one-dimensional constructs parallel to the crystallographic a direction (Fig. 5). The largest difference in unit-cell length between (II) and (III) is for the a axes and is thus associated with small differences in spacing for this hydrogen-bonded motif. In contrast, the only strong hydrogen-bond acceptors in the structure of (I) are the chloride anions. These each accept hydrogen bonds from an O—H group and from two N—H groups (Table 3). One O—H and one N—H donor per chloride ion are from a single DCBZ(H) cation (giving an R₁²(6) motif), but the second N—H donor is from an independent cation and thus the hydrogen bonding propagates to give one-dimensional motifs parallel to the crystallographic a axis (Fig. 6). As (I) is isostructural with Form 1 of [CBZ(H)]Br, this is obviously a hydrogen-bonding system that is common to both the DCBZ(H) and CBZ(H) species. The hydrogen-bonding structure in (II) and (III) (Table 4 and 5) also has precedence in CBZ(H) chemistry, as similar supra­molecular structures are present in both [CBZ(H)]Cl·H₂O and [CBZ(H)]Br·H₂O (Buist et al., 2013, 2015). Thus, although the polymorphic forms of CBZ display different supra­molecular chemistry from the polymorphic forms of DCBZ, the salt forms (as with the cocrystalline forms) of the two APIs have stuctures based around the same inter­molecular hydrogen bonding.

Synthesis and crystallization

DCBZ (0.208 g, 0.87 mmol) and NaI (0.0656 g, 0.44 mmol) were dissolved in warm methanol (4 ml). Once the solution had cooled to room temperature, acetyl chloride (1 ml) was added slowly. The reaction vial was covered with a perforated parafilm seal. Crystals of [DCBZ(H)]Cl were deposited within 48 h. Some of the crystals with their mother liquor were then left in the unsealed vial. After 5 d, the solid present was found to be [DCBZ(H)]Cl·H₂O.

DCBZ (0.198 g, 0.83 mmol) was dissolved in methanol (4 ml). The solution was heated in a water bath until the DCBZ had dissolved. Once the solution had cooled to room temperature, concentrated hydro­bromic acid (1 ml) was added slowly. The reaction test tube was sealed with parafilm. Small holes were made in the parafilm to aid evaporation. Crystals formed over a period of 10 d. The same product was also isolated on reacting a methanol solution of DCBZ with acetyl bromide in the presence of ammonium bromide. Ammonium bromide (here) and NaI (above) were included in attempts to form ionic cocrystalline forms of DCBZ as described for CBZ by Buist & Kennedy (2014).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. For both structures, H atoms bound to C atoms were placed in the expected geometric positions and treated in riding modes, with C—H = 0.95 and 0.99 Å for sp² CH and CH₂ groups, respectively, and with U_iso(H) = 1.2U_eq(C). In (I) and (II), all H atoms bound to N or O atoms were located by difference synthesis and refined isotropically. H atoms bound to N or O atoms in (III) were located and treated similarly, with the exception that it was neccessary to restrain the N—H and O—H distances of the NH₂ and OH₂ groups to 0.88 (2) Å.

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., 1994) for (I), (III); SHELXT (Sheldrick, 2015a) for (II). Program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) for (I), (III); SHELXL2014 (Sheldrick, 2015b) for (II). For all compounds, molecular graphics: Mercury (Macrae et al., 2008) and ORTEP-3 for Windows (Farrugia, 2012). Software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) for (I), (III); SHELXL2014 (Sheldrick, 2015b) for (II).

Figures

	Fig. 1. The molecular structure of salt (I), with non-H atoms shown as 50% probability displacement ellipsoids.
	Fig. 2. The molecular structure of hydrated chloride salt (II), with non-H atoms shown as 50% probability displacement ellipsoids.
	Fig. 3. The molecular structure of hydrated bromide salt (III), with non-H atoms shown as 50% probability displacement ellipsoids.
	Fig. 4. Hydrogen bonding results in dimers of cation–anion pairs in the structure of hydrated chloride salt (II). Hydrated bromide salt (III) is isostructural.
	Fig. 5. The one-dimensional hydrogen-bonded polymer extending parallel to a in the structure of hydrated chloride salt (II).
	Fig. 6. The one-dimensional hydrogen-bonded polymer extending parallel to a in the structure of chloride salt (I).

(I) (10,11-Dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium chloride

Crystal data

C15H15N2O^+·Cl^−	F(000) = 1152
Mr = 274.74	Dx = 1.344 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 10284 reflections
a = 5.4867 (17) Å	θ = 3.2–28.1°
b = 9.8381 (3) Å	µ = 0.27 mm^−1
c = 50.3061 (17) Å	T = 123 K
V = 2715.5 (9) Å^3	Fragment, colourless
Z = 8	0.28 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur E diffractometer	6173 independent reflections
Radiation source: fine-focus sealed tube	5189 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ω scans	θmax = 28.2°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −7→7
Tmin = 0.907, Tmax = 1.000	k = −12→12
28541 measured reflections	l = −64→64

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)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.028P)^2 + 1.1761P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
6173 reflections	Δρmax = 0.29 e Å^−3
367 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Absolute structure: Flack (1983), 2519 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (5)

Special details

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cl1	−0.40173 (13)	−0.32252 (6)	0.093469 (12)	0.02391 (15)
Cl2	0.11444 (13)	1.04391 (6)	0.157770 (13)	0.02736 (16)
O1	−0.0122 (4)	−0.21374 (17)	0.06205 (3)	0.0228 (4)
O2	0.4882 (3)	0.92086 (17)	0.19029 (3)	0.0235 (4)
N1	0.2174 (4)	−0.02588 (19)	0.06253 (4)	0.0157 (4)
N2	0.0385 (4)	−0.1048 (2)	0.10162 (4)	0.0183 (5)
N3	0.7142 (4)	0.7310 (2)	0.18699 (4)	0.0175 (5)
N4	0.5366 (4)	0.8250 (2)	0.14929 (4)	0.0187 (5)
C1	0.2361 (5)	−0.0348 (2)	0.03397 (5)	0.0170 (5)
C2	0.0785 (5)	0.0467 (2)	0.01936 (5)	0.0185 (5)
C3	−0.0934 (5)	0.1391 (3)	0.03395 (5)	0.0230 (6)
H3A	−0.1861	0.0851	0.0471	0.028*
H3B	−0.2116	0.1777	0.0211	0.028*
C4	0.0371 (5)	0.2557 (2)	0.04833 (5)	0.0208 (6)
H4A	0.1075	0.3161	0.0346	0.025*
H4B	−0.0883	0.3091	0.0579	0.025*
C5	0.2375 (5)	0.2227 (2)	0.06800 (5)	0.0172 (5)
C6	0.3180 (4)	0.0931 (2)	0.07535 (5)	0.0148 (5)
C7	0.5036 (4)	0.0739 (2)	0.09362 (5)	0.0180 (5)
H7	0.5562	−0.0156	0.0978	0.022*
C8	0.6135 (5)	0.1846 (2)	0.10587 (5)	0.0212 (5)
H8	0.7379	0.1717	0.1187	0.025*
C9	0.5387 (5)	0.3135 (3)	0.09899 (5)	0.0232 (6)
H9	0.6134	0.3903	0.1071	0.028*
C10	0.3561 (5)	0.3322 (2)	0.08045 (5)	0.0221 (6)
H10	0.3089	0.4222	0.0760	0.027*
C11	0.0932 (5)	0.0388 (3)	−0.00838 (5)	0.0241 (6)
H11	−0.0130	0.0920	−0.0191	0.029*
C12	0.2621 (5)	−0.0464 (3)	−0.02035 (5)	0.0254 (6)
H12	0.2703	−0.0510	−0.0392	0.030*
C13	0.4188 (5)	−0.1248 (3)	−0.00521 (5)	0.0259 (6)
H13	0.5342	−0.1826	−0.0136	0.031*
C14	0.4068 (5)	−0.1188 (2)	0.02225 (5)	0.0217 (5)
H14	0.5143	−0.1715	0.0329	0.026*
C15	0.0810 (5)	−0.1148 (2)	0.07582 (4)	0.0160 (5)
C16	0.8125 (4)	0.6166 (2)	0.17232 (5)	0.0163 (5)
C17	0.7296 (5)	0.4849 (2)	0.17727 (5)	0.0184 (5)
C18	0.5266 (5)	0.4449 (3)	0.19626 (5)	0.0231 (6)
H18A	0.5903	0.3724	0.2080	0.028*
H18B	0.3937	0.4044	0.1856	0.028*
C19	0.4133 (5)	0.5552 (3)	0.21409 (5)	0.0258 (6)
H19A	0.3170	0.6183	0.2029	0.031*
H19B	0.3004	0.5117	0.2269	0.031*
C20	0.7449 (5)	0.7268 (2)	0.21544 (5)	0.0190 (6)
C21	0.6011 (5)	0.6350 (2)	0.22922 (5)	0.0232 (6)
C22	0.6423 (6)	0.6201 (3)	0.25637 (5)	0.0331 (7)
H22	0.5460	0.5584	0.2664	0.040*
C23	0.8233 (6)	0.6951 (3)	0.26887 (5)	0.0382 (8)
H23	0.8527	0.6828	0.2873	0.046*
C24	0.9615 (6)	0.7878 (3)	0.25459 (6)	0.0347 (7)
H24	1.0827	0.8402	0.2633	0.042*
C25	0.9232 (5)	0.8040 (3)	0.22762 (5)	0.0254 (6)
H25	1.0175	0.8669	0.2177	0.030*
C26	0.8478 (5)	0.3804 (3)	0.16360 (5)	0.0222 (6)
H26	0.7993	0.2891	0.1668	0.027*
C27	1.0327 (5)	0.4055 (3)	0.14566 (5)	0.0239 (6)
H27	1.1077	0.3319	0.1366	0.029*
C28	1.1100 (5)	0.5378 (2)	0.14079 (5)	0.0216 (5)
H28	1.2353	0.5556	0.1282	0.026*
C29	1.0009 (5)	0.6431 (2)	0.15459 (5)	0.0195 (5)
H29	1.0549	0.7338	0.1519	0.023*
C30	0.5795 (5)	0.8258 (2)	0.17506 (4)	0.0173 (5)
H1	−0.128 (6)	−0.252 (3)	0.0726 (6)	0.046 (10)*
H1N	−0.066 (5)	−0.170 (3)	0.1087 (5)	0.027 (7)*
H2N	0.086 (5)	−0.037 (3)	0.1121 (6)	0.031 (8)*
H2	0.351 (7)	0.969 (3)	0.1799 (7)	0.068 (11)*
H3N	0.432 (5)	0.890 (3)	0.1436 (5)	0.023 (7)*
H4N	0.579 (6)	0.754 (3)	0.1374 (6)	0.039 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0308 (4)	0.0228 (3)	0.0181 (3)	−0.0075 (3)	0.0056 (3)	−0.0031 (2)
Cl2	0.0361 (4)	0.0263 (3)	0.0197 (3)	0.0120 (3)	−0.0069 (3)	−0.0054 (3)
O1	0.0298 (10)	0.0231 (9)	0.0154 (9)	−0.0111 (8)	0.0050 (8)	−0.0033 (7)
O2	0.0310 (11)	0.0244 (9)	0.0152 (9)	0.0084 (8)	−0.0016 (8)	−0.0039 (7)
N1	0.0216 (11)	0.0161 (10)	0.0094 (10)	−0.0019 (9)	0.0005 (8)	−0.0013 (8)
N2	0.0231 (13)	0.0197 (11)	0.0120 (10)	−0.0054 (10)	0.0025 (9)	−0.0012 (9)
N3	0.0227 (11)	0.0192 (10)	0.0106 (10)	0.0032 (9)	0.0014 (9)	0.0015 (8)
N4	0.0252 (12)	0.0198 (11)	0.0110 (10)	0.0053 (10)	−0.0005 (8)	0.0018 (9)
C1	0.0207 (13)	0.0196 (13)	0.0107 (12)	−0.0045 (11)	0.0006 (10)	−0.0006 (10)
C2	0.0184 (13)	0.0215 (12)	0.0157 (12)	−0.0031 (12)	−0.0008 (11)	0.0004 (10)
C3	0.0191 (13)	0.0324 (14)	0.0175 (12)	0.0034 (13)	−0.0028 (12)	0.0003 (10)
C4	0.0213 (14)	0.0230 (13)	0.0182 (13)	0.0049 (11)	0.0032 (10)	0.0028 (10)
C5	0.0182 (13)	0.0205 (13)	0.0127 (12)	−0.0017 (11)	0.0014 (10)	−0.0010 (10)
C6	0.0189 (13)	0.0155 (11)	0.0101 (11)	−0.0013 (10)	0.0037 (10)	−0.0015 (9)
C7	0.0193 (12)	0.0196 (12)	0.0150 (12)	0.0016 (10)	0.0011 (11)	−0.0015 (10)
C8	0.0174 (13)	0.0291 (13)	0.0171 (12)	−0.0028 (13)	0.0000 (11)	−0.0036 (11)
C9	0.0267 (15)	0.0216 (13)	0.0213 (14)	−0.0055 (12)	0.0034 (11)	−0.0077 (11)
C10	0.0280 (15)	0.0154 (12)	0.0229 (13)	0.0039 (11)	0.0044 (11)	−0.0015 (10)
C11	0.0296 (14)	0.0283 (13)	0.0144 (12)	−0.0022 (14)	−0.0024 (12)	0.0034 (11)
C12	0.0387 (17)	0.0235 (14)	0.0139 (13)	−0.0063 (13)	0.0008 (12)	−0.0026 (11)
C13	0.0315 (15)	0.0241 (13)	0.0223 (13)	−0.0001 (13)	0.0107 (13)	−0.0065 (11)
C14	0.0233 (13)	0.0207 (12)	0.0210 (13)	−0.0015 (12)	−0.0012 (12)	−0.0039 (10)
C15	0.0192 (13)	0.0172 (11)	0.0116 (11)	−0.0002 (11)	−0.0018 (11)	−0.0010 (9)
C16	0.0172 (13)	0.0202 (13)	0.0114 (12)	0.0021 (10)	−0.0024 (10)	−0.0019 (10)
C17	0.0188 (13)	0.0224 (13)	0.0141 (13)	0.0013 (11)	−0.0047 (10)	0.0013 (10)
C18	0.0226 (14)	0.0263 (14)	0.0204 (14)	−0.0018 (12)	−0.0020 (11)	0.0027 (11)
C19	0.0221 (14)	0.0339 (14)	0.0214 (13)	−0.0019 (14)	0.0064 (12)	0.0052 (11)
C20	0.0227 (14)	0.0221 (13)	0.0122 (12)	0.0063 (12)	0.0006 (10)	−0.0007 (10)
C21	0.0281 (14)	0.0260 (13)	0.0156 (12)	0.0077 (13)	0.0016 (12)	−0.0008 (10)
C22	0.050 (2)	0.0356 (15)	0.0139 (13)	0.0120 (15)	0.0049 (14)	0.0062 (12)
C23	0.060 (2)	0.0421 (18)	0.0120 (13)	0.0217 (17)	−0.0097 (13)	−0.0042 (13)
C24	0.0375 (18)	0.0390 (16)	0.0278 (16)	0.0128 (14)	−0.0142 (14)	−0.0104 (13)
C25	0.0249 (14)	0.0289 (14)	0.0224 (13)	0.0055 (13)	−0.0004 (12)	−0.0046 (11)
C26	0.0252 (15)	0.0168 (12)	0.0244 (14)	−0.0003 (11)	−0.0036 (11)	−0.0029 (10)
C27	0.0214 (14)	0.0249 (13)	0.0255 (14)	0.0075 (12)	−0.0028 (11)	−0.0075 (11)
C28	0.0185 (13)	0.0297 (13)	0.0167 (12)	0.0018 (13)	0.0020 (11)	−0.0012 (10)
C29	0.0186 (13)	0.0202 (13)	0.0195 (13)	0.0000 (11)	−0.0018 (11)	0.0007 (10)
C30	0.0192 (13)	0.0194 (12)	0.0134 (11)	−0.0011 (12)	0.0010 (10)	−0.0006 (10)

Geometric parameters (Å, º)

O1—C15	1.300 (3)	C10—H10	0.9500
O1—H1	0.91 (3)	C11—C12	1.387 (4)
O2—C30	1.309 (3)	C11—H11	0.9500
O2—H2	1.03 (4)	C12—C13	1.383 (4)
N1—C15	1.331 (3)	C12—H12	0.9500
N1—C1	1.443 (3)	C13—C14	1.384 (3)
N1—C6	1.446 (3)	C13—H13	0.9500
N2—C15	1.323 (3)	C14—H14	0.9500
N2—H1N	0.93 (3)	C16—C29	1.390 (3)
N2—H2N	0.89 (3)	C16—C17	1.396 (3)
N3—C30	1.333 (3)	C17—C26	1.397 (3)
N3—C20	1.442 (3)	C17—C18	1.519 (3)
N3—C16	1.450 (3)	C18—C19	1.539 (4)
N4—C30	1.318 (3)	C18—H18A	0.9900
N4—H3N	0.90 (3)	C18—H18B	0.9900
N4—H4N	0.95 (3)	C19—C21	1.503 (4)
C1—C14	1.381 (4)	C19—H19A	0.9900
C1—C2	1.389 (3)	C19—H19B	0.9900
C2—C11	1.400 (3)	C20—C25	1.381 (4)
C2—C3	1.502 (3)	C20—C21	1.386 (4)
C3—C4	1.534 (3)	C21—C22	1.392 (3)
C3—H3A	0.9900	C22—C23	1.387 (4)
C3—H3B	0.9900	C22—H22	0.9500
C4—C5	1.514 (3)	C23—C24	1.387 (4)
C4—H4A	0.9900	C23—H23	0.9500
C4—H4B	0.9900	C24—C25	1.382 (4)
C5—C6	1.399 (3)	C24—H24	0.9500
C5—C10	1.406 (3)	C25—H25	0.9500
C6—C7	1.385 (3)	C26—C27	1.380 (4)
C7—C8	1.389 (3)	C26—H26	0.9500
C7—H7	0.9500	C27—C28	1.391 (4)
C8—C9	1.377 (4)	C27—H27	0.9500
C8—H8	0.9500	C28—C29	1.383 (3)
C9—C10	1.381 (4)	C28—H28	0.9500
C9—H9	0.9500	C29—H29	0.9500
C15—O1—H1	106 (2)	C14—C13—H13	120.1
C30—O2—H2	108.2 (19)	C1—C14—C13	118.9 (3)
C15—N1—C1	120.0 (2)	C1—C14—H14	120.5
C15—N1—C6	121.51 (19)	C13—C14—H14	120.5
C1—N1—C6	117.80 (19)	O1—C15—N2	120.6 (2)
C15—N2—H1N	115.6 (16)	O1—C15—N1	116.5 (2)
C15—N2—H2N	125.8 (18)	N2—C15—N1	122.9 (2)
H1N—N2—H2N	118 (2)	C29—C16—C17	122.0 (2)
C30—N3—C20	122.1 (2)	C29—C16—N3	117.3 (2)
C30—N3—C16	121.4 (2)	C17—C16—N3	120.6 (2)
C20—N3—C16	116.08 (19)	C16—C17—C26	116.4 (2)
C30—N4—H3N	115.0 (17)	C16—C17—C18	126.3 (2)
C30—N4—H4N	125.7 (18)	C26—C17—C18	117.3 (2)
H3N—N4—H4N	118 (2)	C17—C18—C19	118.7 (2)
C14—C1—C2	122.8 (2)	C17—C18—H18A	107.6
C14—C1—N1	120.6 (2)	C19—C18—H18A	107.6
C2—C1—N1	116.6 (2)	C17—C18—H18B	107.6
C1—C2—C11	117.4 (2)	C19—C18—H18B	107.6
C1—C2—C3	118.8 (2)	H18A—C18—H18B	107.1
C11—C2—C3	123.8 (2)	C21—C19—C18	112.8 (2)
C2—C3—C4	113.0 (2)	C21—C19—H19A	109.0
C2—C3—H3A	109.0	C18—C19—H19A	109.0
C4—C3—H3A	109.0	C21—C19—H19B	109.0
C2—C3—H3B	109.0	C18—C19—H19B	109.0
C4—C3—H3B	109.0	H19A—C19—H19B	107.8
H3A—C3—H3B	107.8	C25—C20—C21	122.7 (2)
C5—C4—C3	119.1 (2)	C25—C20—N3	120.5 (2)
C5—C4—H4A	107.5	C21—C20—N3	116.7 (2)
C3—C4—H4A	107.5	C20—C21—C22	117.8 (3)
C5—C4—H4B	107.5	C20—C21—C19	118.5 (2)
C3—C4—H4B	107.5	C22—C21—C19	123.6 (3)
H4A—C4—H4B	107.0	C23—C22—C21	120.4 (3)
C6—C5—C10	115.7 (2)	C23—C22—H22	119.8
C6—C5—C4	126.7 (2)	C21—C22—H22	119.8
C10—C5—C4	117.6 (2)	C24—C23—C22	120.4 (3)
C7—C6—C5	122.2 (2)	C24—C23—H23	119.8
C7—C6—N1	117.8 (2)	C22—C23—H23	119.8
C5—C6—N1	120.0 (2)	C25—C24—C23	120.1 (3)
C6—C7—C8	120.4 (2)	C25—C24—H24	120.0
C6—C7—H7	119.8	C23—C24—H24	120.0
C8—C7—H7	119.8	C20—C25—C24	118.7 (3)
C9—C8—C7	118.8 (2)	C20—C25—H25	120.7
C9—C8—H8	120.6	C24—C25—H25	120.7
C7—C8—H8	120.6	C27—C26—C17	122.1 (2)
C8—C9—C10	120.5 (2)	C27—C26—H26	118.9
C8—C9—H9	119.7	C17—C26—H26	118.9
C10—C9—H9	119.7	C26—C27—C28	120.4 (2)
C9—C10—C5	122.3 (2)	C26—C27—H27	119.8
C9—C10—H10	118.8	C28—C27—H27	119.8
C5—C10—H10	118.8	C29—C28—C27	118.7 (2)
C12—C11—C2	120.3 (2)	C29—C28—H28	120.6
C12—C11—H11	119.9	C27—C28—H28	120.6
C2—C11—H11	119.9	C28—C29—C16	120.3 (2)
C13—C12—C11	120.9 (2)	C28—C29—H29	119.9
C13—C12—H12	119.6	C16—C29—H29	119.9
C11—C12—H12	119.6	O2—C30—N4	120.8 (2)
C12—C13—C14	119.7 (3)	O2—C30—N3	116.7 (2)
C12—C13—H13	120.1	N4—C30—N3	122.5 (2)
C15—N1—C1—C14	−86.0 (3)	C30—N3—C16—C29	71.1 (3)
C6—N1—C1—C14	103.5 (3)	C20—N3—C16—C29	−116.4 (2)
C15—N1—C1—C2	95.3 (3)	C30—N3—C16—C17	−112.8 (3)
C6—N1—C1—C2	−75.2 (3)	C20—N3—C16—C17	59.8 (3)
C14—C1—C2—C11	1.6 (4)	C29—C16—C17—C26	0.6 (4)
N1—C1—C2—C11	−179.7 (2)	N3—C16—C17—C26	−175.4 (2)
C14—C1—C2—C3	−177.4 (2)	C29—C16—C17—C18	179.7 (2)
N1—C1—C2—C3	1.3 (3)	N3—C16—C17—C18	3.8 (4)
C1—C2—C3—C4	68.5 (3)	C16—C17—C18—C19	−6.3 (4)
C11—C2—C3—C4	−110.5 (3)	C26—C17—C18—C19	172.8 (2)
C2—C3—C4—C5	−55.4 (3)	C17—C18—C19—C21	−51.4 (3)
C3—C4—C5—C6	−1.5 (4)	C30—N3—C20—C25	−85.2 (3)
C3—C4—C5—C10	178.9 (2)	C16—N3—C20—C25	102.4 (3)
C10—C5—C6—C7	−0.4 (4)	C30—N3—C20—C21	99.7 (3)
C4—C5—C6—C7	180.0 (2)	C16—N3—C20—C21	−72.8 (3)
C10—C5—C6—N1	−176.4 (2)	C25—C20—C21—C22	−0.7 (4)
C4—C5—C6—N1	3.9 (4)	N3—C20—C21—C22	174.3 (2)
C15—N1—C6—C7	70.4 (3)	C25—C20—C21—C19	−179.5 (2)
C1—N1—C6—C7	−119.3 (2)	N3—C20—C21—C19	−4.5 (3)
C15—N1—C6—C5	−113.4 (3)	C18—C19—C21—C20	72.3 (3)
C1—N1—C6—C5	56.9 (3)	C18—C19—C21—C22	−106.5 (3)
C5—C6—C7—C8	1.5 (4)	C20—C21—C22—C23	−0.4 (4)
N1—C6—C7—C8	177.7 (2)	C19—C21—C22—C23	178.4 (3)
C6—C7—C8—C9	−1.7 (4)	C21—C22—C23—C24	1.4 (4)
C7—C8—C9—C10	0.7 (4)	C22—C23—C24—C25	−1.4 (4)
C8—C9—C10—C5	0.5 (4)	C21—C20—C25—C24	0.7 (4)
C6—C5—C10—C9	−0.7 (4)	N3—C20—C25—C24	−174.1 (2)
C4—C5—C10—C9	179.0 (2)	C23—C24—C25—C20	0.3 (4)
C1—C2—C11—C12	−0.8 (4)	C16—C17—C26—C27	−1.5 (4)
C3—C2—C11—C12	178.1 (2)	C18—C17—C26—C27	179.2 (2)
C2—C11—C12—C13	−0.1 (4)	C17—C26—C27—C28	0.7 (4)
C11—C12—C13—C14	0.2 (4)	C26—C27—C28—C29	1.1 (4)
C2—C1—C14—C13	−1.5 (4)	C27—C28—C29—C16	−2.0 (4)
N1—C1—C14—C13	179.9 (2)	C17—C16—C29—C28	1.2 (4)
C12—C13—C14—C1	0.5 (4)	N3—C16—C29—C28	177.3 (2)
C1—N1—C15—O1	5.9 (3)	C20—N3—C30—O2	4.3 (3)
C6—N1—C15—O1	176.0 (2)	C16—N3—C30—O2	176.4 (2)
C1—N1—C15—N2	−173.7 (2)	C20—N3—C30—N4	−175.2 (2)
C6—N1—C15—N2	−3.6 (4)	C16—N3—C30—N4	−3.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1	0.91 (3)	1.96 (3)	2.865 (2)	174 (3)
N2—H1N···Cl1	0.93 (3)	2.49 (3)	3.254 (2)	139 (2)
N2—H2N···Cl2^i	0.89 (3)	2.44 (3)	3.208 (2)	145 (2)
O2—H2···Cl2	1.03 (4)	1.86 (4)	2.889 (2)	173 (3)
N4—H3N···Cl2	0.90 (3)	2.42 (3)	3.192 (2)	144 (2)
N4—H4N···Cl1^ii	0.95 (3)	2.34 (3)	3.179 (2)	148 (2)

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

(II) (10,11-Dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium chloride monohydrate

Crystal data

C15H15N2O^+·Cl^−·H2O	F(000) = 616
Mr = 292.76	Dx = 1.368 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2171 reflections
a = 5.3048 (3) Å	θ = 3.1–29.8°
b = 24.4966 (14) Å	µ = 0.27 mm^−1
c = 11.0163 (6) Å	T = 123 K
β = 96.731 (5)°	Block, colourless
V = 1421.70 (14) Å^3	0.25 × 0.22 × 0.18 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur E diffractometer	3507 independent reflections
Radiation source: fine-focus sealed tube	2477 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω scans	θmax = 29.0°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −7→6
Tmin = 0.967, Tmax = 1.000	k = −29→31
7044 measured reflections	l = −15→14

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0362P)^2 + 0.1996P] where P = (Fo^2 + 2Fc^2)/3
3507 reflections	(Δ/σ)max = 0.001
201 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cl1	0.22098 (8)	0.54240 (2)	0.68704 (4)	0.02364 (13)
O1	0.3193 (2)	0.35371 (5)	0.42865 (12)	0.0195 (3)
O1W	0.2533 (3)	0.40465 (6)	0.23288 (12)	0.0221 (3)
N1	0.5160 (3)	0.36537 (6)	0.61893 (13)	0.0153 (3)
N2	0.2632 (3)	0.43409 (7)	0.52585 (16)	0.0206 (4)
C1	0.5617 (3)	0.39448 (7)	0.73387 (16)	0.0153 (4)
C2	0.4221 (3)	0.37804 (8)	0.82641 (16)	0.0174 (4)
C3	0.2334 (3)	0.33258 (8)	0.80044 (17)	0.0197 (4)
H3A	0.1249	0.3403	0.7230	0.024*
H3B	0.1226	0.3309	0.8667	0.024*
C4	0.3647 (4)	0.27728 (8)	0.79053 (17)	0.0204 (4)
H4A	0.4579	0.2688	0.8715	0.025*
H4B	0.2307	0.2492	0.7738	0.025*
C5	0.5485 (3)	0.27070 (8)	0.69585 (16)	0.0178 (4)
C6	0.6178 (3)	0.31080 (8)	0.61605 (16)	0.0164 (4)
C7	0.6633 (4)	0.21941 (8)	0.68785 (19)	0.0252 (5)
H7	0.6189	0.1908	0.7396	0.030*
C8	0.8387 (4)	0.20906 (9)	0.60743 (19)	0.0283 (5)
H8	0.9121	0.1738	0.6041	0.034*
C9	0.9075 (4)	0.25027 (9)	0.53148 (19)	0.0270 (5)
H9	1.0302	0.2436	0.4770	0.032*
C10	0.7963 (3)	0.30103 (8)	0.53575 (17)	0.0201 (4)
H10	0.8419	0.3294	0.4837	0.024*
C11	0.4745 (4)	0.40282 (8)	0.94024 (17)	0.0227 (4)
H11	0.3804	0.3928	1.0050	0.027*
C12	0.6633 (4)	0.44207 (8)	0.95966 (18)	0.0246 (5)
H12	0.6994	0.4583	1.0381	0.030*
C13	0.7997 (4)	0.45781 (8)	0.86587 (17)	0.0231 (4)
H13	0.9279	0.4849	0.8799	0.028*
C14	0.7491 (3)	0.43393 (8)	0.75109 (17)	0.0188 (4)
H14	0.8412	0.4445	0.6859	0.023*
C15	0.3652 (3)	0.38528 (7)	0.52315 (16)	0.0156 (4)
H1	0.284 (5)	0.3755 (11)	0.355 (2)	0.059 (8)*
H1N	0.288 (4)	0.4565 (10)	0.586 (2)	0.036 (7)*
H1W	0.112 (5)	0.4259 (11)	0.239 (2)	0.055 (8)*
H2N	0.150 (4)	0.4426 (9)	0.463 (2)	0.033 (6)*
H2W	0.381 (5)	0.4265 (11)	0.244 (2)	0.058 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0191 (2)	0.0264 (3)	0.0251 (3)	0.0011 (2)	0.00162 (18)	−0.0048 (2)
O1	0.0249 (7)	0.0190 (7)	0.0142 (7)	−0.0008 (6)	0.0009 (6)	−0.0010 (5)
O1W	0.0223 (7)	0.0255 (8)	0.0185 (7)	0.0008 (7)	0.0023 (6)	0.0008 (6)
N1	0.0181 (7)	0.0154 (8)	0.0128 (7)	0.0002 (6)	0.0031 (6)	−0.0004 (6)
N2	0.0251 (9)	0.0214 (9)	0.0147 (8)	0.0042 (7)	0.0001 (7)	−0.0008 (7)
C1	0.0168 (8)	0.0157 (9)	0.0130 (9)	0.0032 (7)	0.0003 (7)	−0.0015 (7)
C2	0.0169 (9)	0.0181 (10)	0.0168 (9)	0.0019 (8)	0.0005 (7)	0.0008 (7)
C3	0.0175 (9)	0.0237 (10)	0.0187 (10)	−0.0019 (8)	0.0056 (8)	0.0020 (8)
C4	0.0212 (9)	0.0195 (10)	0.0204 (10)	−0.0040 (8)	0.0011 (8)	0.0025 (8)
C5	0.0167 (9)	0.0185 (10)	0.0172 (9)	−0.0024 (8)	−0.0025 (8)	−0.0017 (8)
C6	0.0153 (8)	0.0152 (9)	0.0176 (9)	0.0009 (7)	−0.0026 (7)	−0.0032 (7)
C7	0.0270 (10)	0.0194 (10)	0.0275 (11)	0.0001 (9)	−0.0036 (9)	0.0012 (9)
C8	0.0278 (10)	0.0220 (11)	0.0329 (12)	0.0070 (9)	−0.0055 (10)	−0.0075 (9)
C9	0.0225 (9)	0.0322 (12)	0.0259 (11)	0.0041 (9)	0.0012 (9)	−0.0100 (9)
C10	0.0186 (9)	0.0235 (10)	0.0179 (9)	−0.0022 (8)	0.0006 (8)	−0.0043 (8)
C11	0.0258 (10)	0.0263 (11)	0.0164 (9)	0.0024 (9)	0.0045 (8)	−0.0007 (8)
C12	0.0307 (10)	0.0254 (11)	0.0165 (10)	0.0021 (9)	−0.0020 (8)	−0.0042 (8)
C13	0.0238 (10)	0.0184 (10)	0.0256 (11)	−0.0018 (9)	−0.0039 (8)	−0.0011 (8)
C14	0.0193 (9)	0.0177 (10)	0.0197 (10)	0.0013 (8)	0.0033 (7)	0.0025 (8)
C15	0.0157 (8)	0.0165 (9)	0.0153 (9)	−0.0024 (7)	0.0051 (7)	0.0006 (7)

Geometric parameters (Å, º)

O1—C15	1.297 (2)	C4—H4B	0.9900
O1—H1	0.97 (3)	C5—C6	1.396 (3)
O1W—H1W	0.92 (3)	C5—C7	1.404 (3)
O1W—H2W	0.86 (3)	C6—C10	1.390 (3)
N1—C15	1.339 (2)	C7—C8	1.381 (3)
N1—C6	1.444 (2)	C7—H7	0.9500
N1—C1	1.449 (2)	C8—C9	1.387 (3)
N2—C15	1.314 (2)	C8—H8	0.9500
N2—H1N	0.86 (2)	C9—C10	1.379 (3)
N2—H2N	0.89 (2)	C9—H9	0.9500
C1—C14	1.384 (3)	C10—H10	0.9500
C1—C2	1.388 (2)	C11—C12	1.387 (3)
C2—C11	1.392 (3)	C11—H11	0.9500
C2—C3	1.502 (3)	C12—C13	1.384 (3)
C3—C4	1.533 (3)	C12—H12	0.9500
C3—H3A	0.9900	C13—C14	1.390 (3)
C3—H3B	0.9900	C13—H13	0.9500
C4—C5	1.518 (3)	C14—H14	0.9500
C4—H4A	0.9900
C15—O1—H1	110.2 (16)	C10—C6—N1	117.25 (17)
H1W—O1W—H2W	106 (2)	C5—C6—N1	120.72 (16)
C15—N1—C6	120.69 (14)	C8—C7—C5	122.31 (19)
C15—N1—C1	122.19 (15)	C8—C7—H7	118.8
C6—N1—C1	116.77 (14)	C5—C7—H7	118.8
C15—N2—H1N	124.8 (15)	C7—C8—C9	119.86 (19)
C15—N2—H2N	116.1 (15)	C7—C8—H8	120.1
H1N—N2—H2N	119 (2)	C9—C8—H8	120.1
C14—C1—C2	122.59 (16)	C10—C9—C8	119.46 (19)
C14—C1—N1	120.50 (16)	C10—C9—H9	120.3
C2—C1—N1	116.75 (16)	C8—C9—H9	120.3
C1—C2—C11	117.89 (17)	C9—C10—C6	120.18 (19)
C1—C2—C3	118.43 (16)	C9—C10—H10	119.9
C11—C2—C3	123.59 (17)	C6—C10—H10	119.9
C2—C3—C4	111.75 (15)	C12—C11—C2	120.39 (18)
C2—C3—H3A	109.3	C12—C11—H11	119.8
C4—C3—H3A	109.3	C2—C11—H11	119.8
C2—C3—H3B	109.3	C13—C12—C11	120.62 (18)
C4—C3—H3B	109.3	C13—C12—H12	119.7
H3A—C3—H3B	107.9	C11—C12—H12	119.7
C5—C4—C3	118.47 (16)	C12—C13—C14	119.98 (18)
C5—C4—H4A	107.7	C12—C13—H13	120.0
C3—C4—H4A	107.7	C14—C13—H13	120.0
C5—C4—H4B	107.7	C1—C14—C13	118.52 (18)
C3—C4—H4B	107.7	C1—C14—H14	120.7
H4A—C4—H4B	107.1	C13—C14—H14	120.7
C6—C5—C7	116.23 (17)	O1—C15—N2	121.44 (17)
C6—C5—C4	126.58 (17)	O1—C15—N1	117.00 (16)
C7—C5—C4	117.18 (17)	N2—C15—N1	121.53 (17)
C10—C6—C5	121.94 (18)
C15—N1—C1—C14	−85.0 (2)	C1—N1—C6—C5	58.2 (2)
C6—N1—C1—C14	101.7 (2)	C6—C5—C7—C8	1.1 (3)
C15—N1—C1—C2	99.4 (2)	C4—C5—C7—C8	−178.24 (17)
C6—N1—C1—C2	−73.8 (2)	C5—C7—C8—C9	0.3 (3)
C14—C1—C2—C11	0.3 (3)	C7—C8—C9—C10	−1.1 (3)
N1—C1—C2—C11	175.75 (16)	C8—C9—C10—C6	0.3 (3)
C14—C1—C2—C3	−176.46 (17)	C5—C6—C10—C9	1.2 (3)
N1—C1—C2—C3	−1.0 (2)	N1—C6—C10—C9	177.79 (16)
C1—C2—C3—C4	71.6 (2)	C1—C2—C11—C12	−0.9 (3)
C11—C2—C3—C4	−105.0 (2)	C3—C2—C11—C12	175.67 (18)
C2—C3—C4—C5	−57.9 (2)	C2—C11—C12—C13	1.0 (3)
C3—C4—C5—C6	1.5 (3)	C11—C12—C13—C14	−0.4 (3)
C3—C4—C5—C7	−179.22 (16)	C2—C1—C14—C13	0.2 (3)
C7—C5—C6—C10	−1.9 (2)	N1—C1—C14—C13	−175.05 (16)
C4—C5—C6—C10	177.41 (16)	C12—C13—C14—C1	−0.2 (3)
C7—C5—C6—N1	−178.36 (15)	C6—N1—C15—O1	−0.9 (2)
C4—C5—C6—N1	0.9 (3)	C1—N1—C15—O1	−173.93 (15)
C15—N1—C6—C10	68.2 (2)	C6—N1—C15—N2	177.44 (17)
C1—N1—C6—C10	−118.44 (17)	C1—N1—C15—N2	4.5 (3)
C15—N1—C6—C5	−115.18 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1W	0.97 (3)	1.51 (3)	2.4807 (18)	173 (3)
N2—H1N···Cl1	0.86 (2)	2.42 (3)	3.2151 (19)	153 (2)
N2—H2N···Cl1^i	0.89 (2)	2.45 (2)	3.3192 (18)	168.9 (19)
O1W—H1W···Cl1^i	0.92 (3)	2.17 (3)	3.0513 (16)	159 (2)
O1W—H2W···Cl1^ii	0.86 (3)	2.29 (3)	3.1084 (16)	159 (2)

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

(III) (10,11-Dihydro-5H-dibenzo[b,f]azepin-5-yl)(hydroxy)methylidene]azanium bromide monohydrate

Crystal data

C15H15N2O^+·Br^−·H2O	F(000) = 688
Mr = 337.22	Dx = 1.526 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2990 reflections
a = 5.4857 (2) Å	θ = 3.1–29.2°
b = 24.5526 (9) Å	µ = 2.80 mm^−1
c = 10.9796 (4) Å	T = 123 K
β = 96.931 (3)°	Prism, colourless
V = 1468.02 (9) Å^3	0.25 × 0.20 × 0.15 mm
Z = 4

Data collection

Oxford Diffraction Xcalibur E diffractometer	3324 independent reflections
Radiation source: fine-focus sealed tube	2687 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −7→4
Tmin = 0.794, Tmax = 1.000	k = −27→31
6786 measured reflections	l = −13→14

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0282P)^2 + 0.7435P] where P = (Fo^2 + 2Fc^2)/3
3324 reflections	(Δ/σ)max = 0.001
201 parameters	Δρmax = 0.67 e Å^−3
4 restraints	Δρmin = −0.39 e Å^−3

Special details

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Br1	0.23260 (4)	0.545139 (11)	0.68613 (2)	0.02088 (9)
O1	0.6696 (3)	0.64943 (8)	0.57548 (17)	0.0178 (4)
O1W	0.7590 (3)	0.60056 (8)	0.77670 (17)	0.0209 (4)
N1	0.4675 (3)	0.63562 (9)	0.38819 (18)	0.0139 (4)
N2	0.7246 (4)	0.56885 (10)	0.4784 (2)	0.0194 (5)
C1	0.3659 (4)	0.69024 (10)	0.3908 (2)	0.0152 (5)
C2	0.4346 (4)	0.73025 (11)	0.3119 (2)	0.0177 (6)
C3	0.6149 (5)	0.72373 (11)	0.2181 (3)	0.0224 (6)
H3A	0.7445	0.7516	0.2362	0.027*
H3B	0.5263	0.7325	0.1365	0.027*
C4	0.7425 (5)	0.66865 (11)	0.2077 (2)	0.0208 (6)
H4A	0.8500	0.6706	0.1416	0.025*
H4B	0.8473	0.6609	0.2856	0.025*
C5	0.5615 (4)	0.62304 (11)	0.1805 (2)	0.0159 (5)
C6	0.4244 (4)	0.60684 (10)	0.2730 (2)	0.0144 (5)
C7	0.5138 (5)	0.59752 (12)	0.0668 (2)	0.0238 (6)
H7	0.6057	0.6073	0.0021	0.029*
C8	0.3328 (5)	0.55798 (12)	0.0476 (3)	0.0255 (7)
H8	0.3017	0.5410	−0.0304	0.031*
C9	0.1970 (5)	0.54294 (11)	0.1402 (3)	0.0230 (6)
H9	0.0724	0.5160	0.1255	0.028*
C10	0.2431 (5)	0.56730 (11)	0.2551 (2)	0.0186 (6)
H10	0.1524	0.5571	0.3199	0.022*
C11	0.3226 (5)	0.78114 (12)	0.3188 (3)	0.0270 (7)
H11	0.3655	0.8097	0.2671	0.032*
C12	0.1501 (5)	0.79107 (12)	0.3992 (3)	0.0306 (7)
H12	0.0781	0.8261	0.4025	0.037*
C13	0.0837 (5)	0.74979 (12)	0.4743 (3)	0.0272 (7)
H13	−0.0360	0.7563	0.5283	0.033*
C14	0.1917 (5)	0.69905 (12)	0.4707 (2)	0.0199 (6)
H14	0.1474	0.6705	0.5222	0.024*
C15	0.6217 (4)	0.61702 (10)	0.4822 (2)	0.0146 (5)
H1N	0.844 (4)	0.5600 (13)	0.532 (2)	0.037 (10)*
H1W	0.639 (5)	0.5774 (12)	0.773 (3)	0.051 (11)*
H1	0.708 (6)	0.6333 (15)	0.642 (3)	0.041 (10)*
H2N	0.698 (6)	0.5474 (11)	0.416 (2)	0.034 (9)*
H2W	0.894 (5)	0.5824 (14)	0.777 (3)	0.057 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.01676 (14)	0.02352 (16)	0.02204 (15)	0.00066 (11)	0.00097 (10)	−0.00367 (12)
O1	0.0246 (10)	0.0175 (10)	0.0105 (9)	−0.0003 (8)	−0.0007 (8)	−0.0022 (8)
O1W	0.0215 (10)	0.0240 (11)	0.0172 (10)	−0.0010 (9)	0.0025 (8)	−0.0015 (8)
N1	0.0163 (10)	0.0135 (11)	0.0120 (10)	0.0004 (8)	0.0022 (8)	−0.0011 (9)
N2	0.0245 (12)	0.0185 (13)	0.0144 (12)	0.0052 (10)	−0.0012 (10)	−0.0024 (10)
C1	0.0145 (12)	0.0148 (13)	0.0150 (12)	0.0009 (10)	−0.0040 (10)	−0.0027 (11)
C2	0.0155 (12)	0.0159 (14)	0.0200 (13)	−0.0023 (10)	−0.0047 (11)	−0.0012 (11)
C3	0.0238 (14)	0.0197 (15)	0.0229 (14)	−0.0049 (12)	0.0002 (12)	0.0064 (12)
C4	0.0198 (13)	0.0250 (16)	0.0182 (14)	−0.0047 (11)	0.0052 (11)	0.0032 (12)
C5	0.0168 (12)	0.0167 (14)	0.0145 (13)	0.0010 (10)	0.0026 (10)	0.0021 (11)
C6	0.0160 (12)	0.0152 (13)	0.0112 (12)	0.0034 (10)	−0.0011 (10)	−0.0013 (10)
C7	0.0307 (15)	0.0285 (16)	0.0132 (13)	0.0046 (12)	0.0066 (12)	0.0027 (12)
C8	0.0340 (16)	0.0257 (17)	0.0152 (14)	0.0026 (12)	−0.0037 (12)	−0.0053 (12)
C9	0.0235 (14)	0.0187 (14)	0.0248 (14)	−0.0021 (11)	−0.0047 (11)	−0.0024 (13)
C10	0.0199 (13)	0.0164 (14)	0.0197 (14)	0.0009 (11)	0.0036 (11)	0.0023 (12)
C11	0.0309 (16)	0.0179 (15)	0.0293 (16)	0.0002 (12)	−0.0085 (13)	0.0026 (13)
C12	0.0308 (16)	0.0217 (16)	0.0363 (18)	0.0105 (13)	−0.0080 (14)	−0.0098 (14)
C13	0.0223 (14)	0.0317 (17)	0.0267 (16)	0.0070 (12)	−0.0007 (12)	−0.0104 (14)
C14	0.0185 (13)	0.0234 (15)	0.0175 (13)	−0.0002 (11)	0.0001 (11)	−0.0050 (12)
C15	0.0142 (12)	0.0174 (14)	0.0130 (12)	−0.0025 (10)	0.0051 (10)	0.0006 (11)

Geometric parameters (Å, º)

O1—C15	1.299 (3)	C4—H4B	0.9900
O1—H1	0.84 (3)	C5—C6	1.392 (3)
O1W—H1W	0.868 (18)	C5—C7	1.393 (4)
O1W—H2W	0.861 (18)	C6—C10	1.387 (4)
N1—C15	1.333 (3)	C7—C8	1.386 (4)
N1—C6	1.443 (3)	C7—H7	0.9500
N1—C1	1.454 (3)	C8—C9	1.381 (4)
N2—C15	1.314 (3)	C8—H8	0.9500
N2—H1N	0.855 (18)	C9—C10	1.392 (4)
N2—H2N	0.863 (18)	C9—H9	0.9500
C1—C14	1.390 (4)	C10—H10	0.9500
C1—C2	1.392 (4)	C11—C12	1.391 (4)
C2—C11	1.399 (4)	C11—H11	0.9500
C2—C3	1.519 (4)	C12—C13	1.383 (4)
C3—C4	1.533 (4)	C12—H12	0.9500
C3—H3A	0.9900	C13—C14	1.382 (4)
C3—H3B	0.9900	C13—H13	0.9500
C4—C5	1.502 (4)	C14—H14	0.9500
C4—H4A	0.9900
C15—O1—H1	114 (2)	C10—C6—N1	120.4 (2)
H1W—O1W—H2W	108 (4)	C5—C6—N1	117.0 (2)
C15—N2—H1N	120 (2)	C8—C7—C5	120.3 (2)
C15—N2—H2N	123 (2)	C8—C7—H7	119.8
H1N—N2—H2N	116 (3)	C5—C7—H7	119.8
C15—N1—C6	122.1 (2)	C9—C8—C7	121.0 (3)
C15—N1—C1	120.6 (2)	C9—C8—H8	119.5
C6—N1—C1	116.5 (2)	C7—C8—H8	119.5
C14—C1—C2	122.8 (2)	C8—C9—C10	119.8 (3)
C14—C1—N1	116.8 (2)	C8—C9—H9	120.1
C2—C1—N1	120.4 (2)	C10—C9—H9	120.1
C1—C2—C11	116.3 (2)	C6—C10—C9	118.6 (3)
C1—C2—C3	126.5 (2)	C6—C10—H10	120.7
C11—C2—C3	117.2 (2)	C9—C10—H10	120.7
C2—C3—C4	118.9 (2)	C12—C11—C2	121.9 (3)
C2—C3—H3A	107.6	C12—C11—H11	119.1
C4—C3—H3A	107.6	C2—C11—H11	119.1
C2—C3—H3B	107.6	C13—C12—C11	119.9 (3)
C4—C3—H3B	107.6	C13—C12—H12	120.1
H3A—C3—H3B	107.0	C11—C12—H12	120.1
C5—C4—C3	112.1 (2)	C14—C13—C12	119.9 (3)
C5—C4—H4A	109.2	C14—C13—H13	120.0
C3—C4—H4A	109.2	C12—C13—H13	120.0
C5—C4—H4B	109.2	C13—C14—C1	119.2 (3)
C3—C4—H4B	109.2	C13—C14—H14	120.4
H4A—C4—H4B	107.9	C1—C14—H14	120.4
C6—C5—C7	117.7 (2)	O1—C15—N2	122.0 (2)
C6—C5—C4	118.0 (2)	O1—C15—N1	116.7 (2)
C7—C5—C4	124.2 (2)	N1—C15—N2	121.3 (2)
C10—C6—C5	122.6 (2)
C15—N1—C1—C14	−71.5 (3)	C1—N1—C6—C5	74.8 (3)
C6—N1—C1—C14	118.1 (2)	C6—C5—C7—C8	0.9 (4)
C15—N1—C1—C2	111.5 (3)	C4—C5—C7—C8	−176.0 (3)
C6—N1—C1—C2	−59.0 (3)	C5—C7—C8—C9	−0.2 (4)
C14—C1—C2—C11	1.5 (4)	C7—C8—C9—C10	−0.6 (4)
N1—C1—C2—C11	178.4 (2)	C5—C6—C10—C9	0.0 (4)
C14—C1—C2—C3	−177.4 (2)	N1—C6—C10—C9	176.0 (2)
N1—C1—C2—C3	−0.5 (4)	C8—C9—C10—C6	0.7 (4)
C1—C2—C3—C4	−1.3 (4)	C1—C2—C11—C12	−0.7 (4)
C11—C2—C3—C4	179.8 (2)	C3—C2—C11—C12	178.3 (2)
C2—C3—C4—C5	57.4 (3)	C2—C11—C12—C13	−0.6 (4)
C3—C4—C5—C6	−70.7 (3)	C11—C12—C13—C14	1.0 (4)
C3—C4—C5—C7	106.2 (3)	C12—C13—C14—C1	−0.2 (4)
C7—C5—C6—C10	−0.8 (4)	C2—C1—C14—C13	−1.1 (4)
C4—C5—C6—C10	176.3 (2)	N1—C1—C14—C13	−178.1 (2)
C7—C5—C6—N1	−176.9 (2)	C6—N1—C15—O1	171.6 (2)
C4—C5—C6—N1	0.2 (3)	C1—N1—C15—O1	1.7 (3)
C15—N1—C6—C10	88.3 (3)	C6—N1—C15—N2	−6.6 (4)
C1—N1—C6—C10	−101.4 (3)	C1—N1—C15—N2	−176.5 (2)
C15—N1—C6—C5	−95.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1W	0.84 (3)	1.67 (4)	2.510 (3)	175 (3)
N2—H1N···Br1^i	0.86 (2)	2.58 (2)	3.431 (2)	172 (3)
N2—H2N···Br1^ii	0.86 (2)	2.58 (2)	3.355 (2)	149 (3)
O1W—H1W···Br1	0.87 (2)	2.45 (2)	3.2381 (19)	152 (3)
O1W—H2W···Br1^i	0.86 (2)	2.40 (2)	3.1960 (19)	154 (3)

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