Supramolecular structures of three configurational isomers of 1-phenyl­ethanaminium malate(1–)

In rac-1-phenyl­ethanaminium rac-malate(1−), C₈H₁₂N⁺·C₄H₅O₅⁻, (I), the anions are linked by two inter-anion O—H⋯O hydrogen bonds into sheets generated by a glide plane and hence containing both enantiomers of the anion. The cations are linked to the anion sheets by three N—H⋯O hydrogen bonds, such that cations of R configuration are bonded to one face of the sheet and cations of S configuration are bonded to the other face. In (R)-1-phenyl­ethanaminium (S)-malate(1−), C₈H₁₂N⁺·C₄H₅O₅⁻, (III), the anions are again linked by two O—H⋯O hydrogen bonds, in one of which the H atom is disordered over two sites, into sheets very similar to those in (I) but which are generated in (III) by translation and so contain only a single enantiomer. The cations in (III) are linked to the anion sheets by three N—H⋯O hydrogen bonds, but the cations are bonded to only one face of the anion sheet. Co-crystallization of (R)-1-phenyl­ethanamine with rac-­malic acid gives the salt (R)-1-phenyl­ethanaminium malate(1−) C₈H₁₂N⁺·C₄H₅O₅⁻, (II), with a structure very similar to that of (III) but where only ca 75% of the anion sites are occupied by (S)-malate(1−), with the remaining 25% occupied by (R)-malate(1−). The layers in (II) show a significant displacement along the [001] direction compared with those in (III).

Comment

We have recently compared the supramolecular structures of pairs of salts formed from achiral di­amines and either racemic malic acid or the enantiopure (S)-malic acid (Farrell et al., 2002b). In these salts, there is a marked tendency for those containing just a single enantiomer of the anion to mimic rather closely the centrosymmetric structures adopted by the corresponding salts formed by the racemic acid. Entirely comparable observations have been made with similar series of di­amine salts formed from either racemic tartaric acid or enantiopure (2R,3R)-tartaric acid (Farrell et al., 2002a). We

have now extended this general study to encompass systems in which the amine component is also chiral and for this purpose we have selected 1-phenyl­ethan­amine, PhCH(CH₃)NH₂, which is readily available in both racemic and enantiopure forms. Using this amine and malic acid, C₄H₆O₅, we have now prepared the series of 1:1 salts PhCH(CH₃)NH₃⁺·C₄H₅O₅⁻, using firstly racemic malic acid with both the racemic amine, giving product (I), and the enantiopure (R)-amine, giving product (II), and secondly, enantiopure(S)-malic acid with each of enantiopure (R)-amine, giving product (III), enantiopure (S)-amine, giving product (IV), and the racemic amine, giving product (V). Finally, we have also prepared a single example of a 2:1 salt, viz. 2PhCH(CH₃)NH₃⁺·C₄H₄O₅²⁻, (VI), using the racemic amine and enantiopure (S)-malic acid. Although all six products were readily obtainable in analytically pure form, only (I)–(III) have so far provided crystals suitable for single-crystal X-ray diffraction. We report here the structures of the three isomeric forms, (I)–(III), of 1-phenyl­ethanaminium malate(1−), C₈H₁₂N⁺·C₄H₅O₅⁻, which all have the same composition, but the constitutions and configurations of which are all different. A previous study of a deuterated form of (III) (Bau et al., 1983) was aimed solely at establishing the stereochemical configuration of an enzymatically produced malic acid containing a CHD group, and hence the absolute stereochemistry of the enzymatic formation of malic acid; no details of the supramolecular structure were given. Here, we discuss first the structure of (I) and then, for the sake of convenience, the structure of (III) before that of (II).

Compound (I), prepared from racemic 1-phenyl­ethan­amine and racemic malic acid, crystallizes in the polar space group Cc, with equal numbers of R and S cations and equal numbers of R and S anions in the unit cell. In the selected asymmetric unit (Fig. 1), both ions have the R configuration. Compound (II) (Fig. 2) was prepared using enantiopure (R)-1-phenyl­ethan­amine and racemic malic acid. This compound crystallizes in space group P2₁, but while all the cations have the R configuration, the anion sites are occupied by an approximately 1:3 mixture of (R)-malate and (S)-malate anions, so there has been some selectivity during the crystallization process, with the (S)-malate anions preferred. In compound (III) (Fig. 3), which was prepared from two enantiopure components, the R amine and the S acid, and which also crystallizes in the chiral space group P2₁, only these components are present. Hence, the dominant configuration of the anion is the same in (II) and (III), while the same single enantiomer of the cation is present in both (II) and (III). However, while the supramolecular structures of (II) and (III) are similar, they differ in detail.

In each compound, one H atom has been transferred from the acid to the amine to form the cation [PhCH(CH₃)NH₃]⁺. While the H atoms are all fully ordered in compounds (I) and (II), in compound (III) the remaining carboxyl H in the anion is disordered unequally between the carboxyl atoms O3 and O1, with the corresponding atoms H3 and H1 having site occupancies of 0.87 (4) and 0.13 (4), respectively (Fig. 3). Since the two atoms concerned (O3 adjacent to the major-occupancy site of this disordered H atom and O1 adjacent to the minor-occupancy site) participate in an inter-anion O—H⋯O hydrogen bond, the H-atom component of this bond is disordered over two sites, but the disorder has no influence on the overall supramolecular structure. The anion in (II) exhibits configurational disorder such that both enantiomers share a common set of sites for all O atoms and for the carboxyl atoms C1 and C4 (Fig. 4).

In each of compounds (I)–(III), there is an intramolecular O—H⋯O hydrogen bond within the anion (Figs. 1–3) and this probably exercises some influence on the conformation of the anion. The two ions within each asymmetric unit are linked by a single N—H⋯O hydrogen bond (Tables 1–3).

The anions in (I) form a two-dimensional substructure from which the cations are pendent. Carboxyl atom O3 in the anion at (x, y, z) acts as hydrogen-bond donor to carboxyl­ate atom O1 in the anion at (x − 1, y, z), so generating by translation a C(7) chain (Bernstein et al., 1995) running parallel to the [100] direction. Four chains of this type pass through each unit cell. In addition, hydroxyl atom O5 in the anion at (x, y, z) acts as hydrogen-bond donor to carboxyl atom O4 in the anion at ( + x,  − y,  + z), while atom O5 at ( + x,  − y,  + z) in turn acts as donor to atom O4 at (1 + x, y, 1 + z). Hence, a C(6) chain is produced, running parallel to the [101] direction and generated by the n-glide plane at y = . The [100] and [101] chains generate an (010) sheet built from a single type of R₄⁴(22) ring (Fig. 5). Two anion sheets pass through each unit cell, lying in the domains 0.13 < y < 0.37 and 0.63 < y < 0.83, generated by the n-glide planes at y = and y = , respectively.

The cation is linked to the anion sheet by three N—H⋯O hydrogen bonds (Table 1). Ammonium atom N1 in the cation at (x, y, z) is linked, via atoms H1A, H1B and H1C, respectively, to atom O1 in the anion at (x, y, z), O2 in the anion at (x − ,  − y, z − ) and O5 in the anion at (x − ,  − y, z − ), all three of which lie in the same (010) sheet generated by the y = glide plane. The action of this glide plane produces equal numbers of cations on the two faces of the anion sheet, with the R cations all on one face of the anion sheet and the S cations all on the opposite face, and such that the methyl and phenyl components of the cations fill the laminar spaces between the anion sheets (Fig. 6). Hence, each sheet is effectively tripartite in nature, with a polar central layer sandwiched between two lipophilic layers. There are no direction-specific interactions between the lipophilic components of adjacent sheets. In particular, there are neither X—H⋯π(arene) hydrogen bonds (for any of X = C, N or O) nor aromatic π–π stacking interactions.

Although compound (III) crystallizes in a different space group (P2₁) from that of (I) (Cc), the anion substructure has a very similar overall topology. Carboxyl atom O3 in the anion at (x, y, z) acts as hydrogen-bond donor to carboxyl­ate atom O1 in the anion at (x, y, z − 1), so generating by translation a C(7) chain running parallel to the [001] direction (Fig. 7) [cf. the [100] C(7) chain in compound (I) (Fig. 5)]. Just two chains of this type pass through each unit cell. Hydroxyl atom O5 in the anion at (x, y, z) acts as hydrogen-bond donor to carboxyl atom O4 in the anion at (x − 1, y, z), so generating by translation a C(6) chain running parallel to the [100] direction (Fig. 7) [cf. the [101] C(6) chain in compound (I) (Fig. 5)]. Again, there are two of these chains per unit cell. The combination of the [100] and [001] chains in (III) produces an (010) sheet, entirely analogous to the sheet in (I), except that the chiral sheet in (III) is generated by translation and contains only a single enantiomer, while that in (I) is generated by a glide plane and so contains both enantiomers of the anion. Two sheets of this type pass through each unit cell in (III), in the domains 0.01 < y < 0.11 and 0.51 < y < 0.61, so that these sheets are much thinner than those in compound (I) (Figs. 6 and 8).

The cation in (III) is again linked to the anion sheet by three N—H⋯O hydrogen bonds (Table 2). Atom N1 in the cation at (x, y, z) acts as hydrogen-bond donor, via atoms H1A, H1B and H1C, respectively, to atom O1 in the anion at (x, y, z), O2 at (1 + x, y, z) and O5 at (1 + x, y, 1 + z), all of which lie in the same (010) sheet (Figs. 7 and 8). Hence, by contrast with (I) (Fig. 6), in (III) there are cations linked to only one face of an anion sheet, and all the cations have the same R configuration.

In compound (II) (Fig. 3), the cations all have the R configuration, as in (III), but only ca 75% of the anion sites are occupied by (S)-malate ions and some 25% of these sites are occupied by (R)-malate ions. Compound (II) was prepared from racemic malic acid and hence its formation indicates a modest degree of enantioselectivity during the crystallization process, which in turn implies a modest degree of enantio­selective recognition. Since the two orientations of the anions share a common set of O-atom sites (Fig. 4), we shall, for the sake of convenience and clarity, discuss primarily the effects of the major (S)-enantiomer.

Compounds (II) and (III) both crystallize in space group P2₁. Although their cell dimensions are certainly similar, they are by no means identical. The anion substructures are very similar and both are generated by translation (Tables 2 and 3); however, that in (II) is somewhat displaced relative to that in (III). Detailed comparison of the coordinates of corresponding atoms in (II) and (III) shows that, consistently, the x and y coordinates are very similar, but that the z coordinates are all ca 0.1 greater in (II) (Figs. 7–10). Successive sheets are related by the 2₁ axis, so that the offset between successive sheets differs by ca 0.2z or ca 1.5 Å between (II) and (III). As in (III), the cations in (II) are pendent from only one face of the anion sheet, and the projections of the two structures (Figs. 8 and 10) clearly show the relative displacement of the sheets in the [001] direction.

We note that, while in (II) crystallization of the (R)-amine with the rac-acid gives a preponderance of (S)-malic acid units in the product, all attempts to obtain good quality crystals of the salts containing two enantiopure S components, i.e. the enantiomorph of the R,R salt, have to date been unsuccessful.

Figure 1 The R enantiomers of the independent components in (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 2 The independent components in (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. For the sake of clarity, only the major enantiomer of the anion is shown.

Figure 3 The independent components in (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. In the anion, the H-atom sites adjacent to atoms O1 and O3 have occupancies of 0.13 (4) and 0.87 (4), respectively.

Figure 4 The two enantiomers of the anion in (II). The bonds in the major enantiomer [occupancy 0.745 (8)] are shown as full lines and the bonds unique to the minor enantiomer [occupancy 0.255 (8)] are shown as dashed lines (see text). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 5 Part of the crystal structure of (I), showing the formation of an (010) sheet of anions with cations pendent from it. For the sake of clarity, H atoms bonded to C atoms have been omitted, as have the phenyl and methyl groups in the cation. Atoms marked with an asterisk (*), hash (#), dollar sign ($) or ampersand (&) are at the symmetry positions (x − 1, y, z), ( + x,  − y,  + z), (x − ,  − y, z − ) and ( + x,  − y, z − ), respectively.

Figure 6 A stereoview of part of the crystal structure of (I), showing the tripartite sandwich structure of the (010) sheets. For the sake of clarity, H atoms bonded to C atoms have been omitted.

Figure 7 Part of the crystal structure of (III), showing the formation of an (010) sheet of anions with cations pendent from it. For the sake of clarity, only the major component of the disordered hydrogen bond is shown, and H atoms bonded to C atoms, as well as the phenyl and methyl groups, have been omitted. Atoms marked with an asterisk (*), hash (#) or dollar sign ($) are at the symmetry positions (x, y, z − 1), (x − 1, y, z) and (1 + x, y, z), respectively.

Figure 8 A projection of part of the crystal structure of (III), showing the (010) sheets, with cations pendent from only one face of the anion sheet. For the sake of clarity, only the major component of the disordered hydrogen bond is shown, and H atoms bonded to C atoms have been omitted.

Figure 9 Part of the crystal structure of (II), showing the formation of an (010) sheet of anions with cations pendent from it. For the sake of clarity, only the major component of the disordered anion is shown, and H atoms bonded to C atoms, as well as the phenyl and methyl groups, have been omitted. Atoms marked with an asterisk (*), hash (#) or dollar sign ($) are at the symmetry positions (x, y, z − 1), (x − 1, y, z) and (1 + x, y, z), respectively.

Figure 10 A projection of part of the crystal structure of (II), showing the (010) sheets, with cations pendent from only one face of the anion sheet. For the sake of clarity, only the major component of the disordered anion is shown, and H atoms bonded to C atoms have been omitted.

Experimental

For the synthesis of compounds (I)–(V), equimolar quantities of the appropriate isomers of 1-phenyl­ethan­amine and malic acid were separately dissolved in methanol. The appropriate pairs of solutions were mixed and the mixtures were then set aside to crystallize, providing analytically pure samples of (I)–(V). Analyses, found for (I): C 56.3, H 6.7, N 5.5%; found for (II): C 56.0, H 6.7, N 5.5%; found for (III): C 56.7, H 6.8, N 5.4%; found for (IV): C 57.0, H 6.7, N 5.4%; found for (V): C 56.4, H 7.5, N 5.5%; C₁₂H₁₇NO₅ requires: C 56.5, H 6.7, N 5.5%. For the synthesis of (VI), stoichiometric quantities of racemic 1-phenyl­ethan­amine and (S)-malic acid (2:1 molar ratio) were separately dissolved in methanol. The solutions were mixed and the mixture was then set aside to crystallize, providing analytically pure (VI). Analysis for (VI), found: C 63.5, H 8.0, N 7.4%; C₂₀H₂₈N₂O₅ requires: C 63.8, H 7.5, N 7.4%. Single crystals of compounds (I)–(III) suitable for single-crystal X-ray diffraction were selected directly from the prepared samples. Despite repeated attempts, no suitable crystals of compounds (IV)–(VI) have yet been obtained.

Compound (I)

Crystal data

• C₈H₁₂N⁺·C₄H₅O₅⁻

• M_r = 255.27

• Monoclinic, Cc

• a = 7.5373 (5) Å

• b = 15.0354 (15) Å

• c = 11.6624 (12) Å

• β = 106.811 (5)°

• V = 1265.2 (2) ų

• Z = 4

• D_x = 1.340 Mg m⁻³

• Mo Kα radiation

• Cell parameters from 13 550 reflections

• θ = 2.7–25.0°

• μ = 0.11 mm⁻¹

• T = 150 (1) K

• Plate, colourless

• 0.34 × 0.32 × 0.14 mm

Data collection

• Nonius KappaCCD diffractometer

• φ scans, and ω scans with κ offsets

• 6949 measured reflections

• 1101 independent reflections

• 1037 reflections with I > 2σ(I)

• R_int = 0.134

• θ_max = 25.0°

• h = −8 → 8

• k = −17 → 17

• l = −13 → 13

Refinement

• Refinement on F²

• R[F² > 2σ(F²)] = 0.045

• wR(F²) = 0.121

• S = 1.05

• 1101 reflections

• 168 parameters

• H-atom parameters constrained

• w = 1/[σ²(F_o²) + (0.0795P)² + 0.3357P] where P = (F_o² + 2F_c²)/3

• (Δ/σ)_max = 0.002

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.27 e Å⁻³

• Extinction correction: SHELXL97

• Extinction coefficient: 0.037 (7)

Table 1
Hydrogen-bonding geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1^i	0.84	1.69	2.528 (3)	176
O5—H5⋯O4^ii	0.84	2.12	2.779 (4)	135
O5—H5⋯O2	0.84	2.15	2.650 (3)	118
N1—H1A⋯O1	0.91	1.95	2.822 (4)	159
N1—H1B⋯O2^iii	0.91	1.93	2.817 (4)	163
N1—H1C⋯O5^iv	0.91	2.02	2.917 (4)	167
Symmetry codes: (i) x-1,y,z; (ii) ; (iii) ; (iv) .

Compound (II)

Crystal data

• C₈H₁₂N⁺·C₄H₅O₅⁻

• M_r = 255.27

• Monoclinic, P2₁

• a = 6.4227 (5) Å

• b = 13.5815 (10) Å

• c = 7.5439 (3) Å

• β = 108.665 (4)°

• V = 623.44 (7) ų

• Z = 2

• D_x = 1.360 Mg m⁻³

• Mo Kα radiation

• Cell parameters from 1482 reflections

• θ = 2.9–27.5°

• μ = 0.11 mm⁻¹

• T = 150 (1) K

• Needle, colourless

• 0.32 × 0.14 × 0.12 mm

Data collection

• Nonius KappaCCD diffractometer

• φ scans, and ω scans with κ offsets

• 5426 measured reflections

• 1482 independent reflections

• 1391 reflections with I > 2σ(I)

• R_int = 0.064

• θ_max = 27.4°

• h = −8 → 7

• k = −16 → 17

• l = −9 → 9

Refinement

• Refinement on F²

• R[F² > 2σ(F²)] = 0.036

• wR(F²) = 0.094

• S = 1.04

• 1482 reflections

• 176 parameters

• H-atom parameters constrained

• w = 1/[σ²(F_o²) + (0.0515P)² + 0.0754P] where P = (F_o² + 2F_c²)/3

• (Δ/σ)_max < 0.001

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

• Extinction correction: SHELXL97

• Extinction coefficient: 0.22 (3)

Table 2
Hydrogen-bonding geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1^i	0.84	1.71	2.546 (2)	178
O5—H5⋯O2	0.84	2.11	2.615 (2)	119
O5—H5⋯O4^ii	0.84	2.14	2.755 (2)	129
N1—H1A⋯O1	0.91	1.97	2.882 (2)	177
N1—H1B⋯O2^iii	0.91	1.91	2.815 (2)	177
N1—H1C⋯O5^iv	0.91	2.03	2.869 (2)	152
Symmetry codes: (i) x,y,z-1; (ii) x-1,y,z; (iii) 1+x,y,z; (iv) 1+x,y,1+z.

Compound (III)

Crystal data

• C₈H₁₂N⁺·C₄H₅O₅⁻

• M_r = 255.27

• Monoclinic, P2₁

• a = 6.3350 (2) Å

• b = 13.7876 (6) Å

• c = 7.5572 (2) Å

• β = 107.907 (2)°

• V = 628.10 (4) ų

• Z = 2

• D_x = 1.350 Mg m⁻³

• Mo Kα radiation

• Cell parameters from 1504 reflections

• θ = 2.8–27.5°

• μ = 0.11 mm⁻¹

• T = 150 (1) K

• Block, colourless

• 0.26 × 0.20 × 0.18 mm

Data collection

• Nonius KappaCCD diffractometer

• φ scans, and ω scans with κ offsets

• 5348 measured reflections

• 1504 independent reflections

• 1398 reflections with I > 2σ(I)

• R_int = 0.066

• θ_max = 27.5°

• h = −8 → 7

• k = −17 → 16

• l = −9 → 9

Refinement

• Refinement on F²

• R[F² > 2σ(F²)] = 0.032

• wR(F²) = 0.078

• S = 1.06

• 1504 reflections

• 170 parameters

• H-atom parameters constrained

• w = 1/[σ²(F_o²) + (0.0405P)² + 0.0897P] where P = (F_o² + 2F_c²)/3

• (Δ/σ)_max < 0.001

• Δρ_max = 0.27 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

• Extinction correction: SHELXL97

• Extinction coefficient: 0.042 (12)

Table 3
Hydrogen-bonding geometry (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3^i	0.84	1.73	2.548 (2)	164
O3—H3⋯O1^ii	0.84	1.71	2.548 (2)	176
O5—H5⋯O2	0.84	2.13	2.629 (2)	118
O5—H5⋯O4^iii	0.84	2.17	2.777 (2)	129
N1—H1A⋯O1	0.91	1.96	2.865 (2)	170
N1—H1B⋯O2^iv	0.91	1.92	2.834 (2)	178
N1—H1C⋯O5^v	0.91	2.05	2.877 (2)	151
Symmetry codes: (i) x,y,1+z; (ii) x,y,z-1; (iii) x-1,y,z; (iv) 1+x,y,z; (v) 1+x,y,1+z.

For compound (I), the systematic absences permitted Cc and C2/c as possible space groups. Cc was selected and confirmed by the subsequent analysis. For each of (II) and (III), the systematic absences permitted P2₁ and P2₁/m as possible space groups. In each case, P2₁ was selected and confirmed by the subsequent analysis. In compound (II), the anion was found to be disordered over two orientations, such that all of the O-atom sites and the sites for atoms C1 and C4 were common to both orientations, but with distinct sites for atoms C2 and C3 and their associated H atoms, leading to different stereochemical configurations for the two orientations. The site occupancies for the major S and minor R configurations refined to 0.745 (8) and 0.255 (8), respectively. All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (CH₃), 0.99 (CH₂) or 1.00 Å (aliphatic CH), N—H distances of 0.91 Å and O—H distances of 0.84 Å, and with U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for the methyl groups, and 1.5U_eq(N,O). All H atoms were fully ordered with respect to their parent atoms, except for the residual carboxyl H atom in (III), which was found to be disordered over two sites, one denoted H3 adjacent to O3 and the other denoted H1 adjacent to O1, with occupancies 0.87 (4) and 0.13 (4), respectively. In order to ensure maximum comparability of the structures of (II) and (III), the y coordinate of atom N1 in each was initially fixed at 0.5 and only allowed to refine in the final cycles. In the absence of significant anomalous scattering, the values of the Flack (1983) parameter were indeterminate (Flack & Bernardinelli, 2000). Accordingly, the Friedel-equivalent reflections were merged prior to the final refinements. It was therefore not possible to establish the correct orientation of the structure of (I) relative to the polar-axis directions (Jones, 1986). For both (II) and (III), the correct enantiomorph was selected by reference to the known absolute configuration of the enantiopure amine component.

For all three compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwin­owski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Supporting information

S1. Comment

We have recently compared the supramolecular structures of pairs of salts formed from achiral diamines and either racemic malic acid or the enantiopure (S)-malic acid (Farrell et al., 2002b). In these salts, there is a marked tendency for those containing just a single enantiomer of the anion to mimic rather closely the centrosymmetric structures adopted by the corresponding salts formed by the racemic acid. Entirely comparable observations have been made with similar series of diamine salts formed from either racemic tartaric acid or enantiopure (2R,3R)-tartaric acid (Farrell et al., 2002a). We have now extended this general study to encompass systems in which the amine component is also chiral, and for this purpose we have selected 2-phenylethylamine, PhCH(CH₃)NH₂, which is readily available in both racemic and enantiopure forms. Using this amine and malic acid, C₄H₆O₅, we have now prepared the series of 1:1 salts [PhCH(CH₃)NH₃]⁺·[C₄H₅O₅]⁻, using firstly racemic malic acid with both the racemic amine, giving product (I), and the enantiopure (R)-amine, giving product (II), and secondly, enantiopure(S)-malic acid with each of enantiopure (R)-amine, giving product (III), enantiopure (S)-amine, giving product (IV), and the racemic amine, giving product (V). Finally, we have also prepared a single example of a 2:1 salt, [{PhCH(CH₃)NH₃}⁺]₂·[C₄H₄O₅]²⁻, (VI), using the racemic amine and enantiopure (S)-malic acid. Although all six products were readily obtainable in analytically pure form, only (I)-(III) have so far provided crystals suitable for single-crystal X-ray diffraction. Here, we report the structures of the three isomeric forms, (I)-(III), of 2-phenylethylammonium malate(1-), [C₈H₁₂N]⁺·[C₄H₅O₅]⁻, which all have the same composition, but whose constitutions and configurations are all different. A previous study of a deuterated form of (III) (Bau et al., 1983) was aimed solely at establishing the stereochemical configuration of an enzymically produced malic acid containing a CHD group, and hence the absolute stereochemistry of the enzymatic formation of malic acid; no details of the supramolecular structure were given. Here, we discuss first the structure of (I) and then, for the sake of convenience, the structure of (III) before that of (II). \sch

Compound (I), prepared from racemic 2-phenylethylamine and racemic malic acid, crystallizes in the polar space group Cc with equal numbers of (R) and (S) cations and equal numbers of (R) and (S) anions in the unit cell. In the selected asymmetric unit (Fig. 1), both ions have the (R) configuration. Compound (II) (Fig. 2) was prepared using enantiopure (R)-2-phenylethylamine and racemic malic acid. This compound crystallizes in space group P2₁, but while all the cations have the (R) configuration, the anion sites are occupied by an approximately 1:3 mixture of (R)-malate and (S)-malate anions, so there has been some selectivity during the crystallization process, with the (3)-malate anions preferred. In compound (III) (Fig. 3), which was prepared from two enantiopure components, the (R) amine and the (S) acid, and which also crystallizes in the chiral space group P2₁, only these components are present. Hence, the dominant configuration of the anion is the same in (II) and (III), while the same single enantiomer of the cation is present in both (II) and (III). However, while the supramolecular structures of (II) and (III) are similar, they differ in detail.

In each compound, one H has been transferred from the acid to the amine to form the cation [PhCH(CH₃)NH₃]⁺. While the H atoms are all fully ordered in compounds (I) and (II), in compound (III) the remaining carboxyl H in the anion is disordered unequally between the two carboxyl atoms O3 and O1, with the corresponding atoms H3 and H1 having site occupancies of 0.87 (4) and 0.13 (4), respectively (Fig. 3). Since the two atoms concerned, O3 adjacent to the major-occupancy site of this disordered H and O1 adjacent to the minor-occupancy site, participate in an inter-anion O—H···O hydrogen bond, the H component of this bond is disordered over two sites, but the disorder has no influence on the overall supramolecular structure. The anion in (II) exhibits configurational disorder such that both enantiomers share a common set of sites for all O atoms and for the carboxyl atoms C1 and C4 (Fig. 4).

In each of compounds (I)-(III), there is an intramolecular O—H···O hydrogen bond within the anion (Figs. 1–3) and this probably exercises some influence on the conformation of the anion. The two ions within each asymmetric unit are linked by a single N—H···O hydrogen bond (Tables 1–3).

The anions in (I) form a two-dimensional substructure from which the cations are pendent. Carboxyl atom O3 in the anion at (x, y, z) acts as hydrogen-bond donor to carboxylate atom O1 in the anion at (x − 1, y, z), so generating by translation a C(7) chain (Bernstein et al., 1995) running parallel to the [100] direction. Four chains of this type pass through each unit cell. In addition, hydroxyl atom O5 in the anion at (x, y, z) acts as hydrogen-bond donor to carboxyl atom O4 in the anion at (1/2 + x, 1/2 − y, 1/2 + z), while atom O5 at (1/2 + x, 1/2 − y, 1/2 + z) in turn acts as donor to atom O4 at (1 + x, y, 1 + z). Hence a C(6) chain is produced, running parallel to the [101] direction and generated by the n-glide plane at y = 1/4. The [100] and [101] chains generate an (010) sheet built from a single type of R₄⁴(22) ring (Fig. 5). Two anion sheets pass through each unit cell, lying in the domains 0.13 < y < 0.37 and 0.63 < y < 0.83, generated by the n-glide planes at y = 1/4 and y = 3/4, respectively.

The cation is linked to the anion sheet by three N—H···O hydrogen bonds (Table 1). Ammonium atom N1 in the cation at (x, y, z) is linked, via atoms H1A, H1B and H1C, respectively, to atoms O1 in the anion at (x, y, z), O2 in the anion at (x − 1/2, 1/2 − y, z − 1/2) and O5 in the anion at (x − 1/2, 1/2 − y, z − 1/2), all three of which lie in the same (010) sheet generated by the y = 1/4 glide plane. The action of this glide plane produces equal numbers of cations on the two faces of the anion sheet, with the (R) cations all on one face of the anion sheet and the (S) cations all on the opposite face, and such that the methyl and phenyl components of the cations fill the laminar spaces between the anion sheets (Fig. 6). Hence each sheet is effectively tripartite in nature, with a polar central layer sandwiched between two lipophilic layers. There are no direction-specific interactions between the lipophilic components of adjacent sheets. In particular, there are neither X—H···π(arene) hydrogen bonds (for any of X = C, N or O), nor any aromatic π–π stacking interactions.

Although compound (III) crystallizes in a different space group, P2₁, from that of (I) (Cc), the anion substructure has a very similar overall topology. Carboxyl atom O3 in the anion at (x, y, z) acts as hydrogen-bond donor to carboxylate atom O1 in the anion at (x, y, z − 1), so generating by translation a C(7) chain running parallel to the [001] direction (Fig. 7) {cf. the [100] C(7) chain in compound (I) (Fig. 5)}. Just two chains of this type pass through each unit cell. Hydroxyl atom O5 in the anion at (x, y, z) acts as hydrogen-bond donor to carboxyl atom O4 in the anion at (x − 1, y, z), so generating by translation a C(6) chain running parallel to the [100] direction (Fig. 7) {cf. the [101] C(6) chain in compound (I) (Fig. 5)}. Again, there are two of these chains per unit cell. The combination of the [100] and [001] chains in (III) produces an (010) sheet, entirely analogous to the sheet in (I), except that the chiral sheet in (III) is generated by translation and contains only a single enantiomer, while that in (I) is generated by a glide plane and so contains both enantiomers of the anion. Two sheets of this type pass through each unit cell in (III), in the domains 0.01 < y < 0.11 and 0.51 < y < 0.61, so that these sheets are much thinner than those in compound (I) (Figs. 6 and 8).

The cation in (III) is again linked to the anion sheet by three N—H···O hydrogen bonds (Table 2). Atom N1 in the cation at (x, y, z) acts as hydrogen-bond donor, via atoms H1A, H1B and H1C, respectively, to atoms O1 in the anion at (x, y, z), O2 at (1 + x, y, z) and O5 at (1 + x, y, 1 + z), all of which lie in the same (010) sheet (Figs. 7 and 8). Hence, by contrast with (I) (Fig. 6), in (III) there are cations linked to only one face of an anion sheet, and all of the cations have the same (R) configuration.

In compound (II) (Fig. 3), the cations all have the (R) configuration, as in (III), but only ca 75% of the anion sites are occupied by (S)-malate ions, and some 25% of these sites are occupied by (R)-malate ions. Compound (II) was prepared from racemic malic acid and hence its formation indicates a modest degree of enantioselectivity during the crystallization process, which in turn implies a modest degree of enantioselective recognition. Since the two orientations of the anions share a common set of O atom sites (Fig. 4), we shall, for the sake of convenience and clarity, discuss primarily the effects of the major (S)-enantiomer.

Compounds (II) and (III) both crystallize in space group P2₁. Although their cell dimensions are certainly similar, they are by no means identical. The anion substructures are very similar and both are generated by translation (Tables 2 and 3); however, that in (II) is somewhat displaced relative to that in (III). Detailed comparison of the coordinates of corresponding atoms in (II) and (III) shows that, consistently, the x and y coordinates are very similar, but that the z coordinates are all ca 0.1 greater in (II) (Figs. 7–10). Successive sheets are related by the 2₁ axis, so that the offset between successive sheets differs by ca 0.2z or ca 1.5 Å betweeen (II) and (III). As in (III), the cations in (II) are pendent from only one face of the anion sheet, and the projections of the two structures (Figs. 8 and 10) clearly show the relative displacement of the sheets in the [001] direction.

We note that, while in (II) crystallization of the (R)-amine with the rac-acid gives a preponderance of (S)-malic acid units in the product, all attempts to obtain good quality crystals of the salts containing two enantiopure (S) components, i.e. the enantiomorph of the (R,R) salt, have to date been unsuccessful.

S2. Experimental

For the synthesis of compounds (I)-(V), equimolar quantities of the appropriate isomers of 2-phenylethylamine and malic acid were separately dissolved in methanol. The appropriate pairs of solutions were mixed and the mixtures were then set aside to crystallize, providing analytically pure samples of (I)-(V). Analyses, found for (I): C 56.3, H 6.7, N 5.5%; found for (II): C 56.0, H 6.7, N 5.5%; found for (III): C 56.7, H 6.8, N 5.4%; found for (IV): C 57.0, H 6.7, N 5.4%; found for (V): C 56.4, H 7.5, N 5.5%; C₁₂H₁₇NO₅ requires: C 56.5, H 6.7, N 5.5%. For the synthesis of (VI), stoichiometric quantities of racemic 2-phenylethylamine and (S)-malic acid (2:1 molar ratio) were separately dissolved in methanol. The solutions were mixed and the mixture was then set aside to crystallize, providing analytically pure (VI). Analysis for (VI), found: C 63.5, H 8.0, N 7.4%; C₂₀H₂₈N₂O₅ requires: C 63.8, H 7.5, N 7.4%. Single crystals of compounds (I)-(III), suitable for single-crystal X-ray diffraction, were selected directly from the prepared samples. Despite repeated attempts, no suitable crystals of compounds (IV)-(VI) have yet been obtained.

S3. Refinement

For compound (I), the systematic absences permitted Cc and C2/c as possible space groups. Cc was selected and confirmed by the subsequent analysis. For each of (II) and (III), the systematic absences permitted P2₁ and P2₁/m as possible space groups. In each case, P2₁ was selected and confirmed by the subsequent analysis. In compound (II), the anion was found to be disordered over two orientations, such that all of the O atom sites and the sites for atoms C1 and C4 were common to both orientations, but with distinct sites for atoms C2 and C3 and their associated H atoms, leading to different stereochemical configurations for the two orientations. The site occupancies for the major (S) and minor (R) configurations refined to 0.745 (8) and 0.255 (8), respectively. All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (CH₃), 0.99 (CH₂) or 1.00 Å (aliphatic CH), N—H distances of 0.91 Å and O—H distances of 0.84 Å, and with U_iso(H) = 1.2U_eq(C), or 1.5U_eq(C) for the methyl groups, and 1.5U_eq(N,O). All H atoms were fully ordered with respect to their parent atoms, except for the residual carboxyl H atom in (III), which was found to be disordered over two sites, one denoted H3 adjacent to O3 and the other denoted H1 adjacent to O1, with occupancies 0.87 (4) and 0.13 (4), respectively. In order to ensure maximum comparability of the structures of (II) and (III), the y coordinate of atom N1 in each was initially fixed at 0.5 and only allowed to refine in the final cycles. In the absence of significant anomalous scattering, the values of the Flack parameter (Flack, 1983) were indeterminate (Flack & Bernardinelli, 2000). Accordingly, the Friedel-equivalent reflections were merged prior to the final refinements. It was therefore not possible to establish the correct orientation of the structure of (I) relative to the polar axis directions (Jones, 1986). For both (II) and (III), the correct enantiomorph was selected by reference to the known absolute configuration of the enantiopure amine component.

Computing details

For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The (R) enantiomers of the independent components in (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The independent components in (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. For the sake of clarity, only the major enantiomer of the anion is shown.
	Fig. 3. The independent components in (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. In the anion, the H-atom sites adjacent to atoms O1 and O3 have occupancies 0.13 (4) and 0.87 (4), respectively.
	Fig. 4. The two enantiomers of the anion in (II). The bonds in the major enantiomer [occupancy 0.745 (8)] are shown as full lines and the bonds unique to the minor enantiomer [occupancy 0.255 (8)] are shown as dashed lines (see text). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 5. Part of the crystal structure of (I), showing the formation of an (010) sheet of anions with cations pendent from it. For the sake of clarity, H atoms bonded to C atoms have been omitted, as have the phenyl and methyl groups in the cation. The atoms marked with an asterisk (*), hash (#), dollar sign () or ampersand () are at the symmetry positions (x − 1, y, z), (1/2 + x, 1/2 − y, 1/2 + z), (x − 1/2, 1/2 − y, z − 1/2) and (1/2 + x, 1/2 − y, z − 1/2), respectively.
	Fig. 6. A stereoview of part of the crystal structure of (I), showing the tripartite sandwich structure of the (010) sheets. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 7. Part of the crystal structure of (III), showing the formation of an (010) sheet of anions with cations pendent from it. For the sake of clarity, only the major component of the disordered hydrogen bond is shown, and H atoms bonded to C atoms, as well as the phenyl and methyl groups, have been omitted. The atoms marked with an asterisk (*), hash (#) or dollar sign () are at the symmetry positions (x, y, z − 1), (x − 1, y, z) and (1 + x, y, z), respectively.
	Fig. 8. A projection of part of the crystal structure of (III), showing the (010) sheets, with cations pendent from only one face of the anion sheet. For the sake of clarity, only the major component of the disordered hydrogen bond is shown, and H atoms bonded to C atoms have been omitted.
	Fig. 9. Part of the crystal structure of (II), showing the formation of an (010) sheet of anions with cations pendent from it. For the sake of clarity, only the major component of the disordered anion is shown, and H atoms bonded to C atoms, as well as the phenyl and methyl groups, have been omitted. The atoms marked with an asterisk (*), hash (#) or dollar sign () are at the symmetry positions (x, y, z − 1), (x − 1, y, z) and (1 + x, y, z), respectively.
	Fig. 10. A projection of part of the crystal structure of (II), showing the (010) sheets, with cations pendent from only one face of the anion sheet. For the sake of clarity, only the major component of the disordered anion is shown, and H atoms bonded to C atoms have been omitted.

(I) rac-1-phenylethanaminium rac-malate(1-)

Crystal data

C8H12N^+·C4H5O5^−	F(000) = 544
Mr = 255.27	Dx = 1.340 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 13550 reflections
a = 7.5373 (5) Å	θ = 2.7–25.0°
b = 15.0354 (15) Å	µ = 0.11 mm^−1
c = 11.6624 (12) Å	T = 150 K
β = 106.811 (5)°	Plate, colourless
V = 1265.2 (2) Å^3	0.34 × 0.32 × 0.14 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	1037 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.134
Graphite monochromator	θmax = 25.0°, θmin = 2.7°
ϕ scans, and ω scans with κ offsets	h = −8→8
6949 measured reflections	k = −17→17
1101 independent reflections	l = −13→13

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)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0795P)^2 + 0.3357P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.002
1101 reflections	Δρmax = 0.18 e Å^−3
168 parameters	Δρmin = −0.27 e Å^−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.037 (7)

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

	x	y	z	Uiso*/Ueq
O1	0.6694 (3)	0.17654 (18)	0.6623 (2)	0.0444 (6)
O2	0.7039 (3)	0.21943 (19)	0.8514 (2)	0.0433 (6)
O3	0.0126 (3)	0.1428 (2)	0.7286 (2)	0.0469 (7)
O4	0.0035 (4)	0.1775 (2)	0.5422 (2)	0.0538 (7)
O5	0.3542 (3)	0.27134 (19)	0.8048 (2)	0.0454 (6)
C1	0.6102 (4)	0.2054 (3)	0.7465 (3)	0.0404 (8)
C2	0.4005 (5)	0.2256 (3)	0.7106 (3)	0.0420 (8)
C3	0.2963 (4)	0.1380 (3)	0.6839 (3)	0.0435 (8)
C4	0.0890 (4)	0.1546 (2)	0.6426 (3)	0.0402 (8)
N1	0.5537 (4)	0.19757 (19)	0.4111 (2)	0.0383 (7)
C11	0.3667 (5)	0.0979 (2)	0.2540 (3)	0.0429 (8)
C12	0.4316 (6)	0.1122 (3)	0.1562 (4)	0.0569 (11)
C13	0.3055 (10)	0.1059 (4)	0.0391 (4)	0.0802 (18)
C14	0.1203 (9)	0.0858 (3)	0.0257 (5)	0.0772 (17)
C15	0.0605 (7)	0.0731 (3)	0.1204 (5)	0.0683 (14)
C16	0.1805 (5)	0.0786 (3)	0.2347 (4)	0.0509 (9)
C17	0.4927 (5)	0.1032 (2)	0.3817 (3)	0.0438 (8)
C18	0.6590 (6)	0.0423 (3)	0.4069 (4)	0.0633 (13)
H3	−0.1013	0.1540	0.7030	0.070*
H5	0.4502	0.2786	0.8624	0.068*
H2	0.3670	0.2634	0.6369	0.050*
H3A	0.3340	0.1057	0.6207	0.052*
H3B	0.3279	0.1006	0.7568	0.052*
H1C	0.6350	0.2132	0.3701	0.057*
H1A	0.6099	0.2026	0.4911	0.057*
H1B	0.4533	0.2342	0.3898	0.057*
H12	0.5584	0.1261	0.1670	0.068*
H13	0.3474	0.1153	−0.0294	0.096*
H14	0.0360	0.0812	−0.0524	0.093*
H15	−0.0666	0.0600	0.1096	0.082*
H16	0.1346	0.0691	0.3015	0.061*
H17	0.4180	0.0853	0.4361	0.053*
H18A	0.7349	0.0501	0.4900	0.095*
H18B	0.7330	0.0569	0.3527	0.095*
H18C	0.6171	−0.0196	0.3942	0.095*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0270 (11)	0.0690 (16)	0.0360 (13)	0.0013 (11)	0.0071 (10)	−0.0042 (11)
O2	0.0301 (11)	0.0632 (17)	0.0338 (12)	−0.0023 (10)	0.0051 (9)	−0.0038 (11)
O3	0.0283 (11)	0.0734 (19)	0.0360 (13)	0.0056 (11)	0.0046 (10)	−0.0019 (11)
O4	0.0424 (14)	0.0760 (19)	0.0419 (16)	−0.0072 (12)	0.0101 (12)	0.0090 (13)
O5	0.0281 (11)	0.0595 (15)	0.0466 (15)	−0.0013 (11)	0.0076 (10)	−0.0132 (12)
C1	0.0284 (16)	0.053 (2)	0.0380 (19)	−0.0030 (14)	0.0066 (14)	−0.0051 (15)
C2	0.0277 (15)	0.056 (2)	0.0407 (19)	−0.0018 (15)	0.0075 (13)	−0.0084 (16)
C3	0.0311 (17)	0.052 (2)	0.045 (2)	−0.0023 (15)	0.0069 (14)	−0.0061 (16)
C4	0.0317 (16)	0.0510 (19)	0.037 (2)	−0.0059 (14)	0.0079 (15)	−0.0064 (15)
N1	0.0316 (13)	0.0464 (16)	0.0331 (15)	−0.0002 (12)	0.0033 (11)	0.0003 (12)
C11	0.0471 (19)	0.0407 (19)	0.0328 (18)	0.0001 (15)	−0.0012 (14)	0.0000 (14)
C12	0.069 (3)	0.055 (2)	0.045 (2)	−0.0048 (19)	0.014 (2)	0.0014 (17)
C13	0.147 (6)	0.055 (3)	0.041 (3)	0.004 (3)	0.030 (3)	0.0003 (19)
C14	0.093 (4)	0.052 (3)	0.058 (3)	0.001 (3)	−0.024 (3)	−0.006 (2)
C15	0.064 (3)	0.052 (3)	0.068 (3)	0.003 (2)	−0.015 (2)	−0.005 (2)
C16	0.043 (2)	0.046 (2)	0.054 (2)	−0.0016 (16)	−0.0020 (16)	−0.0073 (17)
C17	0.0379 (17)	0.049 (2)	0.0371 (19)	−0.0022 (15)	−0.0012 (14)	0.0034 (15)
C18	0.049 (2)	0.049 (2)	0.073 (3)	0.0011 (17)	−0.013 (2)	−0.002 (2)

Geometric parameters (Å, º)

O1—C1	1.267 (4)	C11—C12	1.382 (5)
O2—C1	1.241 (4)	C11—C16	1.386 (5)
O3—C4	1.305 (4)	C11—C17	1.519 (5)
O3—H3	0.84	C12—C13	1.424 (7)
O4—C4	1.212 (4)	C12—H12	0.95
O5—C2	1.423 (4)	C13—C14	1.392 (9)
O5—H5	0.84	C13—H13	0.95
C1—C2	1.544 (4)	C14—C15	1.322 (8)
C2—C3	1.518 (5)	C14—H14	0.95
C2—H2	1.00	C15—C16	1.380 (6)
C3—C4	1.517 (4)	C15—H15	0.95
C3—H3A	0.99	C16—H16	0.95
C3—H3B	0.99	C17—C18	1.512 (6)
N1—C17	1.500 (5)	C17—H17	1.00
N1—H1C	0.91	C18—H18A	0.98
N1—H1A	0.91	C18—H18B	0.98
N1—H1B	0.91	C18—H18C	0.98
C4—O3—H3	109.5	C16—C11—C17	119.1 (3)
C2—O5—H5	109.5	C11—C12—C13	118.9 (4)
O2—C1—O1	126.5 (3)	C11—C12—H12	120.5
O2—C1—C2	118.7 (3)	C13—C12—H12	120.5
O1—C1—C2	114.7 (3)	C14—C13—C12	119.4 (4)
O5—C2—C3	110.5 (3)	C14—C13—H13	120.3
O5—C2—C1	110.2 (3)	C12—C13—H13	120.3
C3—C2—C1	108.3 (3)	C15—C14—C13	120.7 (4)
O5—C2—H2	109.3	C15—C14—H14	119.6
C3—C2—H2	109.3	C13—C14—H14	119.6
C1—C2—H2	109.3	C14—C15—C16	120.8 (5)
C4—C3—C2	110.3 (3)	C14—C15—H15	119.6
C4—C3—H3A	109.6	C16—C15—H15	119.6
C2—C3—H3A	109.6	C15—C16—C11	121.3 (4)
C4—C3—H3B	109.6	C15—C16—H16	119.4
C2—C3—H3B	109.6	C11—C16—H16	119.4
H3A—C3—H3B	108.1	N1—C17—C18	110.3 (3)
O4—C4—O3	123.5 (3)	N1—C17—C11	109.7 (3)
O4—C4—C3	124.4 (3)	C18—C17—C11	114.0 (3)
O3—C4—C3	112.2 (3)	N1—C17—H17	107.5
C17—N1—H1C	109.5	C18—C17—H17	107.5
C17—N1—H1A	109.5	C11—C17—H17	107.5
H1C—N1—H1A	109.5	C17—C18—H18A	109.5
C17—N1—H1B	109.5	C17—C18—H18B	109.5
H1C—N1—H1B	109.5	H18A—C18—H18B	109.5
H1A—N1—H1B	109.5	C17—C18—H18C	109.5
C12—C11—C16	118.9 (4)	H18A—C18—H18C	109.5
C12—C11—C17	122.0 (3)	H18B—C18—H18C	109.5
O2—C1—C2—O5	8.9 (5)	C11—C12—C13—C14	0.2 (7)
O1—C1—C2—O5	−170.1 (3)	C12—C13—C14—C15	0.4 (7)
O2—C1—C2—C3	−112.0 (4)	C13—C14—C15—C16	−0.6 (7)
O1—C1—C2—C3	68.9 (4)	C14—C15—C16—C11	0.2 (7)
O5—C2—C3—C4	61.7 (4)	C12—C11—C16—C15	0.4 (6)
C1—C2—C3—C4	−177.5 (3)	C17—C11—C16—C15	180.0 (4)
C2—C3—C4—O4	79.2 (5)	C12—C11—C17—N1	68.2 (4)
C2—C3—C4—O3	−99.7 (4)	C16—C11—C17—N1	−111.4 (4)
C16—C11—C12—C13	−0.6 (6)	C12—C11—C17—C18	−56.0 (5)
C17—C11—C12—C13	179.8 (4)	C16—C11—C17—C18	124.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1^i	0.84	1.69	2.528 (3)	176
O5—H5···O4^ii	0.84	2.12	2.779 (4)	135
O5—H5···O2	0.84	2.15	2.650 (3)	118
N1—H1A···O1	0.91	1.95	2.822 (4)	159
N1—H1B···O2^iii	0.91	1.93	2.817 (4)	163
N1—H1C···O5^iv	0.91	2.02	2.917 (4)	167

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

(II) (R)-1-phenylethanaminium (S)-malate(1-)

Crystal data

C8H12N^+·C4H5O5^−	F(000) = 272
Mr = 255.27	Dx = 1.360 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1482 reflections
a = 6.4227 (5) Å	θ = 2.9–27.5°
b = 13.5815 (10) Å	µ = 0.11 mm^−1
c = 7.5439 (3) Å	T = 150 K
β = 108.665 (4)°	Needle, colourless
V = 623.44 (7) Å^3	0.32 × 0.14 × 0.12 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer	1391 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.064
Graphite monochromator	θmax = 27.4°, θmin = 2.9°
ϕ scans, and ω scans with κ offsets	h = −8→7
5426 measured reflections	k = −16→17
1482 independent reflections	l = −9→9

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)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.094	w = 1/[σ^2(Fo^2) + (0.0515P)^2 + 0.0754P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
1482 reflections	Δρmax = 0.18 e Å^−3
176 parameters	Δρmin = −0.16 e Å^−3
5 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.22 (3)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.2835 (2)	0.56554 (15)	0.52472 (19)	0.0384 (4)
O2	−0.0794 (2)	0.55913 (14)	0.3834 (2)	0.0396 (4)
O3	0.1967 (3)	0.60310 (14)	−0.1758 (2)	0.0418 (4)
O4	0.4973 (3)	0.51581 (17)	−0.0412 (2)	0.0507 (5)
O5	−0.0516 (3)	0.52137 (15)	0.0518 (2)	0.0442 (5)
C1	0.1127 (3)	0.55626 (19)	0.3832 (3)	0.0364 (5)
C2	0.1540 (4)	0.5258 (3)	0.1998 (4)	0.0318 (8)	0.745 (8)
C3	0.3035 (5)	0.6000 (3)	0.1495 (4)	0.0342 (9)	0.745 (8)
C4	0.3444 (4)	0.5657 (2)	−0.0313 (3)	0.0445 (6)
C21	0.1191 (12)	0.5796 (8)	0.1802 (9)	0.035 (2)*	0.255 (8)
C31	0.3321 (13)	0.5373 (8)	0.1634 (10)	0.035 (2)*	0.255 (8)
N1	0.7339 (3)	0.50000 (14)	0.6569 (2)	0.0311 (4)
C11	0.5908 (4)	0.34122 (16)	0.5052 (3)	0.0340 (5)
C12	0.6286 (4)	0.3399 (2)	0.3339 (3)	0.0444 (6)
C13	0.4807 (5)	0.2935 (2)	0.1808 (4)	0.0534 (7)
C14	0.2954 (5)	0.24796 (19)	0.1973 (4)	0.0546 (7)
C15	0.2561 (5)	0.2491 (2)	0.3663 (5)	0.0529 (7)
C16	0.4027 (4)	0.29537 (18)	0.5185 (4)	0.0412 (5)
C17	0.7470 (4)	0.38941 (17)	0.6764 (3)	0.0336 (5)
C18	0.9852 (4)	0.35830 (18)	0.7166 (4)	0.0424 (5)
H3	0.2278	0.5895	−0.2730	0.063*
H5	−0.1551	0.5259	0.0968	0.066*
H2A	0.2250	0.4594	0.2165	0.038*	0.745 (8)
H3A	0.4448	0.6048	0.2525	0.041*	0.745 (8)
H3B	0.2335	0.6658	0.1304	0.041*	0.745 (8)
H21	0.1027	0.6515	0.1504	0.042*	0.255 (8)
H31A	0.3335	0.4648	0.1769	0.042*	0.255 (8)
H31B	0.4599	0.5647	0.2628	0.042*	0.255 (8)
H1A	0.5905	0.5190	0.6179	0.047*
H1B	0.7986	0.5194	0.5715	0.047*
H1C	0.8047	0.5283	0.7695	0.047*
H12	0.7560	0.3707	0.3214	0.053*
H13	0.5071	0.2932	0.0639	0.064*
H14	0.1955	0.2159	0.0924	0.065*
H15	0.1285	0.2183	0.3781	0.063*
H16	0.3745	0.2958	0.6347	0.049*
H17	0.7010	0.3708	0.7867	0.040*
H18A	1.0755	0.3874	0.8352	0.064*
H18B	1.0380	0.3811	0.6153	0.064*
H18C	0.9957	0.2864	0.7252	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0317 (7)	0.0544 (9)	0.0305 (7)	0.0006 (7)	0.0118 (6)	−0.0026 (7)
O2	0.0323 (7)	0.0563 (11)	0.0318 (7)	0.0014 (8)	0.0126 (6)	−0.0007 (7)
O3	0.0392 (8)	0.0571 (10)	0.0338 (8)	0.0036 (7)	0.0184 (7)	−0.0037 (7)
O4	0.0364 (8)	0.0753 (13)	0.0399 (9)	0.0046 (9)	0.0116 (7)	0.0115 (8)
O5	0.0310 (7)	0.0713 (12)	0.0313 (7)	−0.0106 (8)	0.0113 (6)	−0.0063 (7)
C1	0.0351 (10)	0.0470 (13)	0.0288 (9)	−0.0030 (10)	0.0127 (8)	−0.0010 (9)
C2	0.0291 (14)	0.0396 (19)	0.0279 (13)	−0.0019 (12)	0.0108 (11)	−0.0024 (11)
C3	0.0350 (15)	0.0414 (19)	0.0282 (14)	−0.0043 (13)	0.0129 (11)	−0.0039 (11)
C4	0.0304 (10)	0.0739 (16)	0.0313 (10)	−0.0090 (12)	0.0128 (8)	−0.0014 (11)
C1A	0.0351 (10)	0.0470 (13)	0.0288 (9)	−0.0030 (10)	0.0127 (8)	−0.0010 (9)
C4A	0.0304 (10)	0.0739 (16)	0.0313 (10)	−0.0090 (12)	0.0128 (8)	−0.0014 (11)
O5A	0.0310 (7)	0.0713 (12)	0.0313 (7)	−0.0106 (8)	0.0113 (6)	−0.0063 (7)
N1	0.0297 (8)	0.0345 (9)	0.0309 (8)	0.0016 (7)	0.0124 (7)	−0.0017 (7)
C11	0.0321 (10)	0.0325 (10)	0.0366 (10)	0.0009 (9)	0.0101 (9)	−0.0012 (8)
C12	0.0486 (13)	0.0490 (13)	0.0371 (12)	−0.0040 (11)	0.0157 (10)	−0.0045 (10)
C13	0.0707 (18)	0.0464 (14)	0.0378 (12)	0.0014 (13)	0.0099 (12)	−0.0083 (11)
C14	0.0558 (15)	0.0326 (12)	0.0575 (17)	−0.0004 (11)	−0.0068 (12)	−0.0069 (11)
C15	0.0419 (13)	0.0362 (13)	0.0719 (19)	−0.0038 (10)	0.0061 (12)	−0.0017 (12)
C16	0.0363 (11)	0.0344 (12)	0.0531 (13)	−0.0005 (9)	0.0147 (10)	0.0004 (10)
C17	0.0338 (10)	0.0349 (11)	0.0327 (10)	−0.0007 (9)	0.0114 (9)	0.0022 (8)
C18	0.0360 (11)	0.0406 (12)	0.0474 (13)	0.0059 (9)	0.0090 (10)	0.0008 (10)

Geometric parameters (Å, º)

O1—C1	1.269 (2)	N1—H1B	0.91
O2—C1	1.235 (3)	N1—H1C	0.91
O3—C4	1.298 (3)	C11—C12	1.390 (3)
O3—H3	0.84	C11—C16	1.391 (3)
O4—C4	1.215 (3)	C11—C17	1.508 (3)
O5—C2	1.432 (3)	C12—C13	1.389 (4)
O5—H5	0.84	C12—H12	0.95
C1—C2	1.547 (3)	C14—C15	1.376 (4)
C2—C3	1.521 (4)	C14—C13	1.382 (4)
C2—H2A	1.00	C14—H14	0.95
C3—C4	1.541 (3)	C13—H13	0.95
C3—H3A	0.99	C15—C16	1.381 (4)
C3—H3B	0.99	C15—H15	0.95
C21—C31	1.526 (9)	C16—H16	0.95
C21—H21	1.00	C17—C18	1.522 (3)
C31—H31A	0.99	C17—H17	1.00
C31—H31B	0.99	C18—H18A	0.98
N1—C17	1.509 (3)	C18—H18B	0.98
N1—H1A	0.91	C18—H18C	0.98
O2—C1—O1	126.25 (18)	C12—C11—C17	122.4 (2)
O2—C1—C2	117.85 (19)	C16—C11—C17	119.21 (19)
O1—C1—C2	115.44 (18)	C13—C12—C11	120.1 (2)
O5—C2—C3	109.4 (2)	C13—C12—H12	119.9
O5—C2—C1	109.2 (2)	C11—C12—H12	119.9
C3—C2—C1	110.4 (2)	C15—C14—C13	119.8 (2)
O5—C2—H2A	109.3	C15—C14—H14	120.1
C3—C2—H2A	109.3	C13—C14—H14	120.1
C1—C2—H2A	109.3	C14—C13—C12	120.5 (2)
C2—C3—C4	108.7 (2)	C14—C13—H13	119.7
C2—C3—H3A	110.0	C12—C13—H13	119.7
C4—C3—H3A	110.0	C14—C15—C16	119.8 (3)
C2—C3—H3B	110.0	C14—C15—H15	120.1
C4—C3—H3B	110.0	C16—C15—H15	120.1
H3A—C3—H3B	108.3	C15—C16—C11	121.4 (2)
O4—C4—O3	123.7 (2)	C15—C16—H16	119.3
O4—C4—C3	126.4 (2)	C11—C16—H16	119.3
O3—C4—C3	109.8 (2)	C11—C17—N1	110.34 (18)
C31—C21—H21	112.4	C11—C17—C18	113.67 (19)
C21—C31—H31A	110.1	N1—C17—C18	108.49 (18)
C21—C31—H31B	110.1	C11—C17—H17	108.1
H31A—C31—H31B	108.5	N1—C17—H17	108.1
C17—N1—H1A	109.5	C18—C17—H17	108.1
C17—N1—H1B	109.5	C17—C18—H18A	109.5
H1A—N1—H1B	109.5	C17—C18—H18B	109.5
C17—N1—H1C	109.5	H18A—C18—H18B	109.5
H1A—N1—H1C	109.5	C17—C18—H18C	109.5
H1B—N1—H1C	109.5	H18A—C18—H18C	109.5
C12—C11—C16	118.4 (2)	H18B—C18—H18C	109.5
O2—C1—C2—O5	9.2 (4)	C15—C14—C13—C12	0.6 (4)
O1—C1—C2—O5	−178.1 (2)	C11—C12—C13—C14	−0.4 (4)
O2—C1—C2—C3	129.5 (3)	C13—C14—C15—C16	−0.4 (4)
O1—C1—C2—C3	−57.9 (3)	C14—C15—C16—C11	0.0 (4)
O5—C2—C3—C4	−61.0 (3)	C12—C11—C16—C15	0.1 (4)
C1—C2—C3—C4	178.8 (2)	C17—C11—C16—C15	−179.2 (2)
C2—C3—C4—O4	−93.2 (4)	C12—C11—C17—N1	72.2 (3)
C2—C3—C4—O3	90.6 (3)	C16—C11—C17—N1	−108.6 (2)
C16—C11—C12—C13	0.0 (4)	C12—C11—C17—C18	−50.0 (3)
C17—C11—C12—C13	179.3 (2)	C16—C11—C17—C18	129.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1^i	0.84	1.71	2.546 (2)	178
O5—H5···O2	0.84	2.11	2.615 (2)	119
O5—H5···O4^ii	0.84	2.14	2.755 (2)	129
N1—H1A···O1	0.91	1.97	2.882 (2)	177
N1—H1B···O2^iii	0.91	1.91	2.815 (2)	177
N1—H1C···O5^iv	0.91	2.03	2.869 (2)	152

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

(III) (R)-1-phenylethanaminium (S)-malate(1-)

Crystal data

C8H12N^+·C4H5O5^−	F(000) = 272
Mr = 255.27	Dx = 1.350 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1504 reflections
a = 6.3350 (2) Å	θ = 2.8–27.5°
b = 13.7876 (6) Å	µ = 0.11 mm^−1
c = 7.5572 (2) Å	T = 150 K
β = 107.907 (2)°	Block, colourless
V = 628.10 (4) Å^3	0.26 × 0.20 × 0.18 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer	1398 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube	Rint = 0.066
Graphite monochromator	θmax = 27.5°, θmin = 2.8°
ϕ scans, and ω scans with κ offsets	h = −8→7
5348 measured reflections	k = −17→16
1504 independent reflections	l = −9→9

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)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0405P)^2 + 0.0897P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1504 reflections	Δρmax = 0.27 e Å^−3
170 parameters	Δρmin = −0.19 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.042 (12)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.2791 (2)	0.56560 (12)	0.41885 (18)	0.0266 (3)
O2	−0.0872 (2)	0.56439 (11)	0.28078 (18)	0.0257 (3)
O3	0.1887 (2)	0.61312 (11)	−0.28668 (19)	0.0269 (3)
O4	0.4823 (2)	0.52158 (11)	−0.14464 (19)	0.0278 (3)
O5	−0.0580 (2)	0.51704 (12)	−0.04784 (17)	0.0263 (3)
C1	0.1074 (3)	0.55516 (14)	0.2801 (2)	0.0201 (4)
C2	0.1460 (3)	0.52752 (14)	0.0962 (2)	0.0199 (4)
C3	0.2915 (3)	0.60348 (15)	0.0421 (3)	0.0233 (4)
C4	0.3327 (3)	0.57550 (14)	−0.1385 (2)	0.0208 (4)
N1	0.7292 (2)	0.50000 (12)	0.5580 (2)	0.0219 (4)
C11	0.5824 (3)	0.34513 (14)	0.3985 (3)	0.0231 (4)
C12	0.6161 (3)	0.35574 (15)	0.2261 (3)	0.0259 (4)
C13	0.4729 (4)	0.31159 (15)	0.0691 (3)	0.0292 (5)
C14	0.2978 (4)	0.25585 (16)	0.0841 (3)	0.0330 (5)
C15	0.2612 (4)	0.24555 (16)	0.2542 (3)	0.0343 (5)
C16	0.4042 (3)	0.28966 (16)	0.4105 (3)	0.0298 (4)
C17	0.7371 (3)	0.39112 (16)	0.5722 (3)	0.0253 (4)
C18	0.9765 (4)	0.35799 (17)	0.6121 (3)	0.0344 (5)
H1	0.2420	0.5707	0.5160	0.040*	0.13 (4)
H3	0.2243	0.5984	−0.3815	0.040*	0.87 (4)
H5	−0.1637	0.5250	−0.0041	0.039*
H2	0.2255	0.4639	0.1135	0.024*
H3A	0.2173	0.6675	0.0276	0.028*
H3B	0.4350	0.6089	0.1420	0.028*
H1A	0.5857	0.5203	0.5276	0.033*
H1B	0.7889	0.5194	0.4686	0.033*
H1C	0.8081	0.5262	0.6692	0.033*
H12	0.7373	0.3933	0.2154	0.031*
H13	0.4956	0.3198	−0.0485	0.035*
H14	0.2024	0.2246	−0.0228	0.040*
H15	0.1389	0.2085	0.2641	0.041*
H16	0.3798	0.2818	0.5275	0.036*
H17	0.6862	0.3719	0.6800	0.030*
H18A	1.0308	0.3772	0.5090	0.052*
H18B	0.9841	0.2873	0.6255	0.052*
H18C	1.0686	0.3881	0.7274	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0210 (6)	0.0418 (8)	0.0163 (6)	0.0019 (6)	0.0047 (5)	−0.0015 (6)
O2	0.0199 (6)	0.0371 (8)	0.0210 (6)	0.0003 (6)	0.0078 (5)	−0.0001 (6)
O3	0.0247 (7)	0.0393 (8)	0.0171 (6)	0.0071 (6)	0.0070 (5)	0.0014 (6)
O4	0.0229 (7)	0.0353 (8)	0.0262 (7)	0.0057 (6)	0.0091 (5)	0.0023 (6)
O5	0.0174 (6)	0.0427 (8)	0.0183 (6)	−0.0034 (6)	0.0046 (5)	−0.0053 (6)
C1	0.0216 (8)	0.0209 (9)	0.0182 (8)	0.0005 (7)	0.0067 (6)	0.0016 (7)
C2	0.0184 (8)	0.0240 (9)	0.0170 (8)	−0.0005 (7)	0.0050 (6)	0.0001 (7)
C3	0.0219 (9)	0.0290 (10)	0.0192 (9)	−0.0061 (8)	0.0068 (7)	−0.0026 (8)
C4	0.0166 (8)	0.0281 (10)	0.0183 (8)	−0.0042 (7)	0.0060 (6)	−0.0005 (7)
N1	0.0188 (7)	0.0273 (9)	0.0197 (7)	−0.0003 (6)	0.0060 (6)	−0.0030 (6)
C11	0.0205 (9)	0.0222 (9)	0.0253 (9)	0.0020 (7)	0.0051 (7)	−0.0008 (8)
C12	0.0260 (10)	0.0248 (10)	0.0261 (10)	−0.0014 (8)	0.0069 (8)	−0.0018 (8)
C13	0.0359 (11)	0.0242 (10)	0.0262 (10)	0.0041 (9)	0.0074 (8)	−0.0021 (8)
C14	0.0319 (11)	0.0234 (10)	0.0361 (12)	0.0008 (8)	−0.0005 (9)	−0.0045 (8)
C15	0.0282 (11)	0.0270 (11)	0.0442 (13)	−0.0049 (9)	0.0058 (9)	0.0010 (9)
C16	0.0264 (10)	0.0302 (11)	0.0346 (11)	−0.0001 (9)	0.0121 (8)	0.0015 (9)
C17	0.0265 (10)	0.0253 (9)	0.0236 (10)	−0.0008 (8)	0.0068 (8)	0.0017 (8)
C18	0.0285 (11)	0.0355 (12)	0.0332 (11)	0.0068 (9)	0.0006 (9)	−0.0015 (9)

Geometric parameters (Å, º)

O1—C1	1.266 (2)	C11—C16	1.389 (3)
O1—H1	0.84	C11—C12	1.391 (3)
O2—C1	1.241 (2)	C11—C17	1.515 (3)
O3—C4	1.314 (2)	C12—C13	1.392 (3)
O3—H3	0.84	C12—H12	0.95
O4—C4	1.217 (2)	C13—C14	1.382 (3)
O5—C2	1.418 (2)	C13—H13	0.95
O5—H5	0.84	C14—C15	1.382 (3)
C1—C2	1.531 (2)	C14—H14	0.95
C2—C3	1.532 (3)	C15—C16	1.388 (3)
C2—H2	1.00	C15—H15	0.95
C3—C4	1.516 (3)	C16—H16	0.95
C3—H3A	0.99	C17—C18	1.522 (3)
C3—H3B	0.99	C17—H17	1.00
N1—C17	1.505 (3)	C18—H18A	0.98
N1—H1A	0.91	C18—H18B	0.98
N1—H1B	0.91	C18—H18C	0.98
N1—H1C	0.91
C1—O1—H1	109.5	C12—C11—C17	121.52 (18)
C4—O3—H3	109.5	C11—C12—C13	120.30 (19)
C2—O5—H5	109.5	C11—C12—H12	119.9
O2—C1—O1	125.94 (17)	C13—C12—H12	119.9
O2—C1—C2	117.73 (15)	C14—C13—C12	120.2 (2)
O1—C1—C2	116.33 (15)	C14—C13—H13	119.9
O5—C2—C1	111.08 (14)	C12—C13—H13	119.9
O5—C2—C3	110.23 (15)	C15—C14—C13	120.1 (2)
C1—C2—C3	110.45 (15)	C15—C14—H14	120.0
O5—C2—H2	108.3	C13—C14—H14	120.0
C1—C2—H2	108.3	C14—C15—C16	119.6 (2)
C3—C2—H2	108.3	C14—C15—H15	120.2
C4—C3—C2	110.53 (16)	C16—C15—H15	120.2
C4—C3—H3A	109.5	C15—C16—C11	121.1 (2)
C2—C3—H3A	109.5	C15—C16—H16	119.5
C4—C3—H3B	109.5	C11—C16—H16	119.5
C2—C3—H3B	109.5	N1—C17—C11	110.94 (16)
H3A—C3—H3B	108.1	N1—C17—C18	108.84 (17)
O4—C4—O3	123.60 (17)	C11—C17—C18	112.69 (17)
O4—C4—C3	122.79 (17)	N1—C17—H17	108.1
O3—C4—C3	113.59 (16)	C11—C17—H17	108.1
C17—N1—H1A	109.5	C18—C17—H17	108.1
C17—N1—H1B	109.5	C17—C18—H18A	109.5
H1A—N1—H1B	109.5	C17—C18—H18B	109.5
C17—N1—H1C	109.5	H18A—C18—H18B	109.5
H1A—N1—H1C	109.5	C17—C18—H18C	109.5
H1B—N1—H1C	109.5	H18A—C18—H18C	109.5
C16—C11—C12	118.73 (18)	H18B—C18—H18C	109.5
C16—C11—C17	119.74 (18)
O2—C1—C2—O5	0.1 (2)	C11—C12—C13—C14	−0.8 (3)
O1—C1—C2—O5	179.44 (17)	C12—C13—C14—C15	1.5 (3)
O2—C1—C2—C3	122.75 (18)	C13—C14—C15—C16	−1.5 (3)
O1—C1—C2—C3	−57.9 (2)	C14—C15—C16—C11	0.8 (3)
O5—C2—C3—C4	−57.7 (2)	C12—C11—C16—C15	−0.2 (3)
C1—C2—C3—C4	179.19 (15)	C17—C11—C16—C15	−179.15 (19)
C2—C3—C4—O4	−85.8 (2)	C16—C11—C17—N1	−116.9 (2)
C2—C3—C4—O3	92.7 (2)	C12—C11—C17—N1	64.2 (2)
C16—C11—C12—C13	0.2 (3)	C16—C11—C17—C18	120.8 (2)
C17—C11—C12—C13	179.14 (19)	C12—C11—C17—C18	−58.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^i	0.84	1.73	2.548 (2)	164
O3—H3···O1^ii	0.84	1.71	2.548 (2)	176
O5—H5···O2	0.84	2.13	2.629 (2)	118
O5—H5···O4^iii	0.84	2.17	2.777 (2)	129
N1—H1A···O1	0.91	1.96	2.865 (2)	170
N1—H1B···O2^iv	0.91	1.92	2.834 (2)	178
N1—H1C···O5^v	0.91	2.05	2.877 (2)	151

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

 

Footnotes

‡Permanent address: Department of Chemistry, University of Guelph, Guelph, Ontario, Canada N1G 2W1.