Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616001133/yf3097sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616001133/yf3097Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616001133/yf3097IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229616001133/yf3097IIIsup4.hkl |
CCDC references: 1448390; 1448389; 1448388
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 NaI 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).
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).
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 Uiso(H) = 1.2Ueq(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.
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—Nring bonds shorten by 0.01–0.04 and 0.03–0.06 Å, respectively. The larger change for C—Nring 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—Nring 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.
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 NaI 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—Nring bonds shorten by 0.01–0.04 and 0.03–0.06 Å, respectively. The larger change for C—Nring 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—Nring 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.
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).
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 Uiso(H) = 1.2Ueq(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.
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).
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) Å3 | Fragment, colourless |
Z = 8 | 0.28 × 0.20 × 0.18 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.028P)2 + 1.1761P] where P = (Fo2 + 2Fc2)/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) |
C15H15N2O+·Cl− | V = 2715.5 (9) Å3 |
Mr = 274.74 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.4867 (17) Å | µ = 0.27 mm−1 |
b = 9.8381 (3) Å | T = 123 K |
c = 50.3061 (17) Å | 0.28 × 0.20 × 0.18 mm |
Oxford Diffraction Xcalibur E diffractometer | 6173 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | 5189 reflections with I > 2σ(I) |
Tmin = 0.907, Tmax = 1.000 | Rint = 0.058 |
28541 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | Δρmax = 0.29 e Å−3 |
S = 1.06 | Δρmin = −0.24 e Å−3 |
6173 reflections | Absolute structure: Flack (1983), 2519 Friedel pairs |
367 parameters | Absolute structure parameter: 0.00 (5) |
0 restraints |
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. |
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)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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···Cl2i | 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···Cl1ii | 0.95 (3) | 2.34 (3) | 3.179 (2) | 148 (2) |
Symmetry codes: (i) x, y−1, z; (ii) x+1, y+1, z. |
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) Å3 | 0.25 × 0.22 × 0.18 mm |
Z = 4 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0362P)2 + 0.1996P] where P = (Fo2 + 2Fc2)/3 |
3507 reflections | (Δ/σ)max = 0.001 |
201 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C15H15N2O+·Cl−·H2O | V = 1421.70 (14) Å3 |
Mr = 292.76 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.3048 (3) Å | µ = 0.27 mm−1 |
b = 24.4966 (14) Å | T = 123 K |
c = 11.0163 (6) Å | 0.25 × 0.22 × 0.18 mm |
β = 96.731 (5)° |
Oxford Diffraction Xcalibur E diffractometer | 3507 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | 2477 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 1.000 | Rint = 0.032 |
7044 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.27 e Å−3 |
3507 reflections | Δρmin = −0.27 e Å−3 |
201 parameters |
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. |
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)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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···Cl1i | 0.89 (2) | 2.45 (2) | 3.3192 (18) | 168.9 (19) |
O1W—H1W···Cl1i | 0.92 (3) | 2.17 (3) | 3.0513 (16) | 159 (2) |
O1W—H2W···Cl1ii | 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. |
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) Å3 | 0.25 × 0.20 × 0.15 mm |
Z = 4 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0282P)2 + 0.7435P] where P = (Fo2 + 2Fc2)/3 |
3324 reflections | (Δ/σ)max = 0.001 |
201 parameters | Δρmax = 0.67 e Å−3 |
4 restraints | Δρmin = −0.39 e Å−3 |
C15H15N2O+·Br−·H2O | V = 1468.02 (9) Å3 |
Mr = 337.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.4857 (2) Å | µ = 2.80 mm−1 |
b = 24.5526 (9) Å | T = 123 K |
c = 10.9796 (4) Å | 0.25 × 0.20 × 0.15 mm |
β = 96.931 (3)° |
Oxford Diffraction Xcalibur E diffractometer | 3324 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | 2687 reflections with I > 2σ(I) |
Tmin = 0.794, Tmax = 1.000 | Rint = 0.028 |
6786 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 4 restraints |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.67 e Å−3 |
3324 reflections | Δρmin = −0.39 e Å−3 |
201 parameters |
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. |
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)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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···Br1i | 0.86 (2) | 2.58 (2) | 3.431 (2) | 172 (3) |
N2—H2N···Br1ii | 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···Br1i | 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. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C15H15N2O+·Cl− | C15H15N2O+·Cl−·H2O | C15H15N2O+·Br−·H2O |
Mr | 274.74 | 292.76 | 337.22 |
Crystal system, space group | Orthorhombic, P212121 | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 123 | 123 | 123 |
a, b, c (Å) | 5.4867 (17), 9.8381 (3), 50.3061 (17) | 5.3048 (3), 24.4966 (14), 11.0163 (6) | 5.4857 (2), 24.5526 (9), 10.9796 (4) |
α, β, γ (°) | 90, 90, 90 | 90, 96.731 (5), 90 | 90, 96.931 (3), 90 |
V (Å3) | 2715.5 (9) | 1421.70 (14) | 1468.02 (9) |
Z | 8 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.27 | 0.27 | 2.80 |
Crystal size (mm) | 0.28 × 0.20 × 0.18 | 0.25 × 0.22 × 0.18 | 0.25 × 0.20 × 0.15 |
Data collection | |||
Diffractometer | Oxford Diffraction Xcalibur E | Oxford Diffraction Xcalibur E | Oxford Diffraction Xcalibur E |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2014) | Multi-scan (CrysAlis PRO; Agilent, 2014) | Multi-scan (CrysAlis PRO; Agilent, 2014) |
Tmin, Tmax | 0.907, 1.000 | 0.967, 1.000 | 0.794, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28541, 6173, 5189 | 7044, 3507, 2477 | 6786, 3324, 2687 |
Rint | 0.058 | 0.032 | 0.028 |
(sin θ/λ)max (Å−1) | 0.665 | 0.682 | 0.650 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.093, 1.06 | 0.044, 0.099, 1.03 | 0.036, 0.078, 1.02 |
No. of reflections | 6173 | 3507 | 3324 |
No. of parameters | 367 | 201 | 201 |
No. of restraints | 0 | 0 | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.24 | 0.27, −0.27 | 0.67, −0.39 |
Absolute structure | Flack (1983), 2519 Friedel pairs | ? | ? |
Absolute structure parameter | 0.00 (5) | ? | ? |
Computer programs: CrysAlis PRO (Agilent, 2014), SIR92 (Altomare et al., 1994), SHELXT (Sheldrick, 2015a), SHELXL97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015b), Mercury (Macrae et al., 2008) and ORTEP-3 for Windows (Farrugia, 2012).
Compound | C—O | C—NH2 | C—Nring | Conformation |
Cl salt ion A in (I) | 1.300 (3) | 1.323 (3) | 1.331 (3) | syn |
Cl salt ion B in (I) | 1.309 (3) | 1.318 (3) | 1.333 (3) | syn |
Cl hydrate salt (II) | 1.297 (2) | 1.314 (2) | 1.339 (2) | anti |
Br hydrate salt (III) | 1.299 (3) | 1.314 (2) | 1.333 (3) | anti |
MeSO3 salt | 1.3005 (17) | 1.3101 (19) | 1.3390 (19) | anti |
DCBZ polymorph I | 1.219 | 1.338 | 1.377 | anti |
DCBZ polymorph II | 1.234 | 1.349 | 1.384 | anti |
DCBZ polymorph III | 1.233 | 1.337 | 1.392 | anti |
DCBZ polymorph IV | 1.252 | 1.333 | 1.380 | syn |
Acetic acid solvate | 1.247 | 1.343 | 1.366 | anti |
Formic acid solvate | 1.248 | 1.341 | 1.370 | anti |
Formamide solvate | 1.245 | 1.345 | 1.366 | anti |
DMSO solvate | 1.236 | 1.339 | 1.382 | mixed |
Saccharin cocrystal | 1.253 | 1.340 | 1.369 | anti |
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···Cl2i | 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···Cl1ii | 0.95 (3) | 2.34 (3) | 3.179 (2) | 148 (2) |
Symmetry codes: (i) x, y−1, z; (ii) x+1, y+1, z. |
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···Cl1i | 0.89 (2) | 2.45 (2) | 3.3192 (18) | 168.9 (19) |
O1W—H1W···Cl1i | 0.92 (3) | 2.17 (3) | 3.0513 (16) | 159 (2) |
O1W—H2W···Cl1ii | 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. |
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···Br1i | 0.855 (18) | 2.582 (18) | 3.431 (2) | 172 (3) |
N2—H2N···Br1ii | 0.863 (18) | 2.58 (2) | 3.355 (2) | 149 (3) |
O1W—H1W···Br1 | 0.868 (18) | 2.45 (2) | 3.2381 (19) | 152 (3) |
O1W—H2W···Br1i | 0.861 (18) | 2.40 (2) | 3.1960 (19) | 154 (3) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1. |
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