The hydro­chloride and hydro­bromide salt forms of (S)-amphetamine

Despite the high profile of amphetamine, there have been relatively few structural studies of its salt forms. The lack of any halide salt forms is surprising as the typical synthetic route for amphetamine initially produces the chloride salt. (S)-Amphetamine hydro­chloride [systematic name: (2S)-1-phenyl­propan-2-aminium chloride], C₉H₁₄N⁺·Cl⁻, has a Z′ = 6 structure with six independent cation–anion pairs. That these are indeed crystallographically independent is supported by different packing orientations of the cations and by the observation of a wide range of cation conformations generated by rotation about the phen­yl–CH₂ bond. The supra­molecular contacts about the anions also differ, such that both a wide variation in the geometry of the three N—H...Cl hydrogen bonds formed by each chloride anion and differences in C—H...Cl contacts are apparent. (S)-Amphetamine hydro­bromide [systematic name: (2S)-1-phenyl­propan-2-aminium bromide], C₉H₁₄N⁺·Br⁻, is broadly similar to the hydro­chloride in terms of cation conformation, the existence of three N—H...X hydrogen-bond contacts per anion and the overall two-dimensional hydrogen-bonded sheet motif. However, only the chloride structure features organic bilayers and Z′ > 1.

S1. Introduction

Salt selection or salt screening is a common technique used in the pharmacuetical industry to improve the physicochemical properties of potential Active Pharmaceutical Ingredients (APIs; Stahl & Wermuth, 2008). Studies of a systematic series of crystal structures of phenyl­ethyl­amine salts have been instigated with a view to determining relationships between crystal structure and the physicochemical properties of APIs (see, for example, Kennedy et al., 2011; Black et al., 2007; Briggs et al., 2012; Cruickshank et al., 2013). The ultimate goal of such studies is to understand and improve the pharmaceutical salt selection process. A member of the phenyl­ethyl­amine class of molecules, amphetamine is popularly known as a stimulant and as a drug of abuse (Kilminster et al., 1977), but it also has legitimate pharmaceutical roles, for instance, in the treatment of attention defecit hyperactivity disorder and narcolepsy (Wood et al., 2014). Despite the high profile of amphetamine, there have been relatively few structural studies of its salt forms. The sulfate has been crystallographically characterized and has been shown to undergo a temperature-dependent phase transition (Pogorzelec-Glaser et al., 2009), and additionally the crystal structures of a di­hydrogen phosphate salt and a salt formed with a pyrazole derivative are known (Hebert, 1978; Reviriego et al., 2006). The lack of any halide salt forms is surprising as the typical synthetic route for amphetamine initially produces the chloride salt. Additionally, the chloride salt is sometimes found in general circulation, although the sulfate salt is that most commonly seized by law enforcement agencies (United Nations, 2006). Structures are known for the chloride salts of structurally related drugs of abuse, such as methyl­amphetamine (Hakey et al., 2008) and the more complex ring-substituted species methyl­ene­dioxy­methamphetamine (MDMA or ecstacy) and ethyl­one (Morimoto et al., 1998; Cameron et al., 2015).

The reaction of (S)-amphetamine free base with aqueous HCl or HBr gave (S)-amphetamine hydro­chloride, (I), and (S)-amphetamine hydro­bromide, (II), respectively. The structures of these two salts are reported here.

S2. Experimental

S2.1. Synthesis and crystallization

(S)-Amphetamine sulfate (0.25 g) was dissolved in deionized water (3 ml) . The pH of the solution was raised to approximately 12.5 by addition of sodium hydroxide solution and the organic product was extracted into di­ethyl ether (5 ml). Allowing the ether to evaporate yielded amphetamine free base as an oily residue. This oil was mixed with water (2 ml), a few drops of either concentrated HCl or HBr were added and the resulting solution was warmed slightly. After several days of slow evaporation, colourless crystals of salts (I) and (II) had developed.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystallographic measurements for (I) and (II) were carried out by the National Crystallography Service (Coles & Gale, 2012). The data for (I) was treated as a nonmerohedral twin by 180° rotation about [001]. Applying the twin matrix (1 0 0 0 1 0.682 0 0 1) within the CrystalClear software (Rigaku, 2012) gave a reflection file in SHELX hklf 5 format. The BASF parameter refined to 0.4431 (6). For both structures, H atoms bound to C atoms were placed in expected geometric positions and treated in riding modes, with C—H = 0.95, 0.98, 0.99 and 1.00 Å for sp²-CH, methyl, CH₂ and sp³-CH, respectively, and with U_iso(H) = 1.5U_eq(C) for methyl groups and 1.2U_eq(C) otherwise. In (I), the H atoms of the NH₃ groups were similarly modelled, with N—H = 0.91 Å and U_iso(H) = 1.5U_eq(N). However, for (II), H atoms bound to N were refined isotropically (see Tables 3 and 4).

S3. Results and discussion

Hydro­chloride salt (I) is unusual in that it crystallizes with six cations and six anions per unit cell in the space group P1 (Z = Z' = 6) (Fig. 1). Structures with Z' > 1 have attracted much attention for their ability to shed light on fundamental aspects of crystal theory (Steed & Steed, 2015; Bernstein et al., 2008). As discussed in the review by Steed & Steed (2015), hydro­chloride salt (I) is in some ways a typical example of the type of species that gives Z' > 1 structures, being as it is a relatively small and enanti­opure organic compound that crystallizes in the space group P1. Note that the diffraction data for (I) were nonmerohedrally twinned by a 180° rotation about [001]. This could be worrying as the presence of unidentified twinning can lead to false identification of structures with Z' > 1 (see, for example, Herbstein, 1964). However, inspection of Fig. 2 shows that a Z' = 1 structure is not correct here. The cations in the layers parallel to the ac plane form two independent rows parallel to the c direction. In each row, every third cation has a different orientation from the others, being rotated by approximately 180 ° along its phenyl-to-NH₃ axis.

The six independent cations of hydro­chloride salt (I) also show distinct conformational variation. This is most easily seen with the C2—C3—C4—C5 and C2—C3—C4—C9 torsion angles (and their equivalents in other ions), which range from -61.9 (5) to -69.3 (4)° and from 106.9 (4) to 115.4 (4)° for five of the six cations (see Table 2). The geometry of the sixth cation, i.e. that containing atom N5, lies significantly outside this range with equivalent angles from -52.7 (4) to 127.5 (3) °. The cations all have anti conformations with N—C—C—C torsion angles within 3.5° of 180°. The previously described crystal structures of salt forms of amphetamine all have similar anti conformations (Hebert, 1978; Pogorzelec-Glaser et al., 2009; Reviriego et al., 2006), as does solution-phase amphetamine (Neville et al., 1971). The structure of the hydro­bromide salt (II) is shown in Fig. 3. Here the C2–C3–C4–C5 and C2–C3–C4–C9 torsion angles are -75.2 (2) and 104.5 (2)°. These values lie outside the range seen for hydro­chloride salt (I). The gle N1–C2–C3–C4 torsion angle is 158.84 (17)° for (II) and this too shows a modest conformational change from the range found for the cations of (I). These small differences do not, however, amount to evidence of two or more dramatically distinct conformer geometries, as has been described previously for salt forms of related phenyl­ethyl­amine species, such as methyl­ephedrine, pseudo-ephedrine and tyramine (Kennedy et al., 2011; Black et al., 2007; Briggs et al., 2012).

All six crystallographically independent NH₃ groups in hydro­chloride salt (I) utilize all three H atoms as single hydrogen-bond donors. Both the H₂PO₄ salt and the room-temperature phase of the SO₄ salt show similar hydrogen-bonding behaviour by the amphetamine cation (Pogorzelec-Glaser et al., 2009; Hebert, 1978). Each NH₃ group in (I) thus forms hydrogen bonds to three chloride anions, two of which are related to one another by translational symmetry, with the third being independent (see Table 3). Although each anion and each cation is involved in three hydrogen-bonding inter­actions, there are subtle differences in the geometry. These are best shown by comparing the environment of atom Cl1 with that of Cl5. The N—H···Cl angles involving Cl5 are all nearly linear (169–171°), whilst the three angles about Cl1 are 145, 159 and 168°. There are further small differences, for instance, atom Cl2 makes a much shorter contact with a phenyl ring than any other chloride anion [C19—H19···Cl2 = 2.72 and 3.562 (5) Å for the H···Cl and C···Cl distances, respectively]. Atom Cl5 has a similar but longer inter­action, whilst the other four anions do not make any such contact. N—H···Cl hydrogen bonds link all six fragments parallel to the crystallographic a and c directions. Both cations and anions act as three-connected nodes and so each two-dimensional hydrogen-bonded sheet can be described as a net with (6,3) topology. The packing structure can be seen in Fig. 2, note the organic bilayers and the hydro­phobic and hydro­philic layers that alternate parallel to the b axis.

Despite the larger size of bromide as compared to chloride, each bromide anion in (II) also forms three hydrogen bonds with three amphetamine cations (Table 4). As the cations also act as three-connected nodes, this structure, like that of (I), features a net with (6,3) topology. In this case, the two-dimensional hydrogen-bonded sheets are parallel to the ab plane. In contrast to (I), there are no C—H···X contacts of less than the sum of van der Waals radii in (II). Fig. 4 shows the resulting packing. Like (I), there are alternating hydro­phobic and hydro­philic layers, but the structure of (II) lacks the organic bilayers found in (I).

There are now structures available for five mineral-acid-derived salt forms of (S)-amphetamine, viz. the chloride, bromide and di­hydrogen phosphate forms, together with the high- and low-temperature sulfate forms. All are layer structures with two-dimensional hydrogen-bonded hydro­philic layers alternating with organic hydro­phobic layers. A Mercury (Macrae et al., 2008) packing analysis of the cation positions of the five structures suggests that, on this basis, only the two sulfate structures are related, having 18 matching cation positions from a cluster of 20 cations (r.m.s. deviation = 0.791 Å. The difference between the two sulfate structures is as follows. Like (I), both sulfate structures consist of organic bilayers. However, the low-temperature sulfate structure has two structurally distinct organic bilayers constructed from four crystallographically independent amphetamine cations (see Fig. 5), whereas in the high-temperature form, all cations and hence all the organic layers are identical. The Mercury packing analysis is thus highlighting the close match between the cation packing of the high-temperature form and the cation packing in only one of the two organic bilayers of the low-temperature form. The packing in the second bilayer is different. Whilst the structures of hydro­chloride salt (I) and the sulfate salt both feature organic bilayers, the structures of hydro­bromide salt (II) and the H₂PO₄ salt do not. It is inter­esting that of the three bilayer structures, two have Z' > 1 and the third is disordered. Both of the other structures have Z' = 1 and are well ordered. Within these five structures, the formation of organic bilayers is correlated with an inability to form simple Z' = 1 ordered structures.

Although in all five salt structures each hydro­philic layer is inter­connected by hydrogen bonds between cations and anions (and for the H₂PO₄ salt between anions and anions too), there are few strong or close contacts within the organic layers. There are some weak C—H···π contacts which seem to be influential in the transformation between the two sulfate phases [see Pogorzelec-Glaser et al. (2009) for a discussion]. All the structures form cation stacks within the organic layers, but the constituent cations in each case are too far apart to form a bonded supra­molecular motif. The exception is hydro­bromide salt (II). Here, a close π–π contact does exist [the shortest C···C distance is 3.388 (3) Å for C6···C9(x+1, y, z)] and this connects stacks of cations parallel to the crystallographic a direction.

Computing details

For both compounds, data collection: CrystalClear-SM Expert (Rigaku, 2012); cell refinement: CrystalClear-SM Expert (Rigaku, 2012); data reduction: CrystalClear-SM Expert (Rigaku, 2012). Program(s) used to solve structure: SIR92 (Altomare et al., 1994 for (I); SIR97 (Altomare et al., 1994 for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of hydrochloride salt (I), with the non-H atoms shown as 50% probability displacement ellipsoids.
	Fig. 2. The packing structure of hydrochloride salt (I), viewed down the crystallographic a direction. The red and blue ellipsoids highlight the different cation orientations found in a cation row parallel to c. The neighbouring cation row of the same organic bilayer has a simlar 2-to-1 arrangement of cation orientations.
	Fig. 3. The molecular structure of hydrobromide salt (II), with the non-H atoms shown as 50% probability displacement ellipsoids.
	Fig. 4. The packing structure of hydrobromide salt (II), viewed down the crystallographic a direction. Note that the organic bilayers shown in Fig. 3 are absent here.
	Fig. 5. The packing structure of the low-temperature form of (S)-amphetamine sulfate drawn from (Pogorzelec-Glaser et al., 2009). Note that the organic bilayers at c = 0 and c = 1 differ from the bilayer at c = 0.5.

(I) (2S)-1-Phenylpropan-2-aminium chloride

Crystal data

C9H14N^+·Cl^−	Z = 6
Mr = 171.66	F(000) = 552
Triclinic, P1	Dx = 1.167 Mg m^−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6396 (4) Å	Cell parameters from 24532 reflections
b = 16.3917 (11) Å	θ = 2.1–27.5°
c = 16.9602 (12) Å	µ = 0.33 mm^−1
α = 69.427 (4)°	T = 100 K
β = 89.995 (5)°	Blade, colourless
γ = 87.286 (5)°	0.18 × 0.06 × 0.01 mm
V = 1465.98 (18) Å^3

Data collection

Rigaku Saturn724+ (2x2 bin mode) diffractometer	19328 independent reflections
Radiation source: fine-focus sealed tube	17180 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.0000
Detector resolution: 28.5714 pixels mm^-1	θmax = 29.8°, θmin = 1.5°
profile data from ω–scans	h = −7→7
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012)	k = −22→22
Tmin = 0.593, Tmax = 1.000	l = −23→22
19328 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.055	H-atom parameters constrained
wR(F^2) = 0.129	w = 1/[σ^2(Fo^2) + (0.070P)^2 + 0.9426P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
19328 reflections	Δρmax = 0.60 e Å^−3
608 parameters	Δρmin = −0.31 e Å^−3
3 restraints	Absolute structure: Flack (1983), with 7328 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (4)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl1	−0.06769 (12)	1.62848 (5)	0.75422 (6)	0.02168 (17)
Cl2	0.53180 (13)	1.80851 (5)	0.53529 (6)	0.02264 (18)
Cl3	0.06999 (12)	1.61130 (5)	0.42734 (5)	0.01902 (16)
Cl4	0.41074 (12)	1.78429 (5)	0.20307 (5)	0.01911 (16)
Cl5	0.80481 (13)	1.59774 (5)	0.10755 (5)	0.02096 (17)
Cl6	0.27312 (12)	1.80318 (5)	−0.14216 (5)	0.02188 (17)
N1	0.2889 (5)	1.61990 (18)	1.00800 (18)	0.0206 (6)
H1A	0.4237	1.6091	1.0403	0.031*
H1B	0.1600	1.6125	1.0417	0.031*
H1C	0.2850	1.6757	0.9708	0.031*
N2	0.7768 (5)	1.81575 (18)	0.76431 (19)	0.0231 (6)
H2A	0.9174	1.8162	0.7905	0.035*
H2B	0.7879	1.7752	0.7390	0.035*
H2C	0.6596	1.8023	0.8030	0.035*
N3	0.4294 (5)	1.62596 (18)	0.67440 (17)	0.0176 (6)
H3A	0.5599	1.6148	0.7088	0.026*
H3B	0.2964	1.6246	0.7051	0.026*
H3C	0.4372	1.6796	0.6338	0.026*
N4	0.0460 (5)	1.79490 (17)	0.45030 (18)	0.0189 (6)
H4A	0.1729	1.8016	0.4803	0.028*
H4B	0.0523	1.7398	0.4491	0.028*
H4C	−0.0906	1.8043	0.4751	0.028*
N5	0.5642 (5)	1.60012 (17)	0.34301 (17)	0.0172 (6)
H5A	0.4378	1.6004	0.3763	0.026*
H5B	0.5403	1.6431	0.2919	0.026*
H5C	0.6984	1.6095	0.3677	0.026*
N6	−0.0844 (5)	1.77880 (17)	0.12398 (17)	0.0182 (6)
H6A	0.0471	1.7787	0.1551	0.027*
H6B	−0.0951	1.7253	0.1196	0.027*
H6C	−0.2158	1.7913	0.1496	0.027*
C1	0.5080 (7)	1.5677 (3)	0.9095 (3)	0.0304 (9)
H1D	0.5137	1.6283	0.8710	0.046*
H1E	0.5085	1.5288	0.8770	0.046*
H1F	0.6469	1.5529	0.9476	0.046*
C2	0.2852 (6)	1.5573 (2)	0.9602 (2)	0.0203 (7)
H2	0.1446	1.5733	0.9209	0.024*
C3	0.2596 (6)	1.4649 (2)	1.0243 (2)	0.0228 (7)
H3D	0.3895	1.4511	1.0670	0.027*
H3E	0.1072	1.4628	1.0538	0.027*
C4	0.2671 (6)	1.3968 (2)	0.9828 (2)	0.0203 (7)
C5	0.0827 (6)	1.3923 (2)	0.9303 (2)	0.0218 (7)
H5	−0.0537	1.4309	0.9220	0.026*
C6	0.0963 (6)	1.3318 (2)	0.8898 (2)	0.0233 (8)
H6	−0.0311	1.3290	0.8543	0.028*
C7	0.2959 (6)	1.2751 (2)	0.9009 (3)	0.0226 (8)
H7	0.3054	1.2338	0.8732	0.027*
C8	0.4794 (7)	1.2797 (2)	0.9526 (2)	0.0244 (8)
H8	0.6153	1.2410	0.9608	0.029*
C9	0.4681 (6)	1.3400 (2)	0.9928 (2)	0.0215 (8)
H9	0.5974	1.3430	1.0274	0.026*
C11	0.6831 (8)	1.9714 (3)	0.7410 (3)	0.0401 (10)
H11A	0.8307	1.9747	0.7700	0.060*
H11B	0.5562	1.9535	0.7821	0.060*
H11C	0.6392	2.0288	0.6990	0.060*
C12	0.7190 (7)	1.9059 (3)	0.6978 (2)	0.0289 (8)
H12	0.5661	1.9034	0.6691	0.035*
C13	0.9113 (7)	1.9288 (3)	0.6319 (2)	0.0299 (8)
H13A	0.9293	1.8826	0.6070	0.036*
H13B	1.0646	1.9319	0.6589	0.036*
C14	0.8476 (7)	2.0172 (2)	0.5618 (2)	0.0292 (8)
C15	0.9846 (8)	2.0886 (3)	0.5489 (3)	0.0479 (12)
H15	1.1239	2.0830	0.5822	0.057*
C16	0.9201 (9)	2.1672 (3)	0.4881 (3)	0.0502 (13)
H16	1.0156	2.2156	0.4798	0.060*
C17	0.7193 (7)	2.1771 (3)	0.4391 (2)	0.0342 (9)
H17	0.6785	2.2315	0.3962	0.041*
C18	0.5783 (7)	2.1078 (2)	0.4525 (3)	0.0368 (9)
H18	0.4352	2.1150	0.4207	0.044*
C19	0.6437 (7)	2.0277 (2)	0.5121 (3)	0.0356 (9)
H19	0.5489	1.9793	0.5194	0.043*
C21	0.6330 (6)	1.5667 (2)	0.5781 (2)	0.0235 (8)
H21A	0.6239	1.6241	0.5331	0.035*
H21B	0.6340	1.5210	0.5532	0.035*
H21C	0.7789	1.5604	0.6115	0.035*
C22	0.4206 (6)	1.5584 (2)	0.6341 (2)	0.0157 (6)
H22	0.2732	1.5702	0.5983	0.019*
C23	0.4086 (6)	1.4677 (2)	0.7034 (2)	0.0227 (7)
H23A	0.5530	1.4557	0.7396	0.027*
H23B	0.2697	1.4678	0.7390	0.027*
C24	0.3889 (6)	1.3964 (2)	0.6675 (2)	0.0192 (7)
C25	0.1894 (6)	1.3917 (2)	0.6201 (3)	0.0270 (8)
H25	0.0620	1.4341	0.6117	0.032*
C26	0.1718 (6)	1.3279 (2)	0.5856 (2)	0.0272 (8)
H26	0.0332	1.3263	0.5544	0.033*
C27	0.3570 (6)	1.2656 (2)	0.5963 (2)	0.0230 (8)
H27	0.3461	1.2215	0.5723	0.028*
C28	0.5574 (6)	1.2685 (2)	0.6422 (2)	0.0261 (8)
H28	0.6856	1.2266	0.6495	0.031*
C29	0.5706 (6)	1.3334 (2)	0.6780 (2)	0.0235 (7)
H29	0.7077	1.3342	0.7102	0.028*
C31	−0.1718 (7)	1.8495 (2)	0.3151 (2)	0.0286 (9)
H31A	−0.1736	1.7897	0.3151	0.043*
H31B	−0.1710	1.8905	0.2569	0.043*
H31C	−0.3133	1.8620	0.3432	0.043*
C32	0.0519 (6)	1.8592 (2)	0.3622 (2)	0.0173 (7)
H32	0.1942	1.8440	0.3340	0.021*
C33	0.0743 (6)	1.9512 (2)	0.3631 (2)	0.0214 (7)
H33A	−0.0604	1.9657	0.3941	0.026*
H33B	0.2228	1.9533	0.3933	0.026*
C34	0.0766 (6)	2.0180 (2)	0.2751 (2)	0.0201 (7)
C35	0.2649 (6)	2.0187 (2)	0.2217 (2)	0.0243 (8)
H35	0.3973	1.9786	0.2420	0.029*
C36	0.2624 (7)	2.0769 (2)	0.1395 (3)	0.0281 (8)
H36	0.3936	2.0767	0.1044	0.034*
C37	0.0690 (6)	2.1358 (2)	0.1077 (2)	0.0244 (8)
H37	0.0669	2.1752	0.0511	0.029*
C38	−0.1205 (7)	2.1360 (2)	0.1599 (2)	0.0252 (8)
H38	−0.2535	2.1757	0.1392	0.030*
C39	−0.1148 (6)	2.0778 (2)	0.2431 (2)	0.0214 (7)
H39	−0.2443	2.0789	0.2786	0.026*
C51	0.6355 (6)	1.4427 (2)	0.4188 (2)	0.0221 (7)
H51A	0.7810	1.4542	0.4438	0.033*
H51B	0.6528	1.3852	0.4131	0.033*
H51C	0.5011	1.4437	0.4551	0.033*
C52	0.5907 (5)	1.5130 (2)	0.3317 (2)	0.0169 (6)
H52	0.7312	1.5129	0.2957	0.020*
C53	0.3662 (6)	1.5002 (2)	0.2866 (2)	0.0210 (7)
H53A	0.2261	1.5023	0.3212	0.025*
H53B	0.3453	1.5488	0.2319	0.025*
C54	0.3771 (6)	1.4147 (2)	0.2712 (2)	0.0199 (7)
C55	0.1915 (6)	1.3571 (2)	0.2974 (2)	0.0270 (8)
H55	0.0617	1.3712	0.3268	0.032*
C56	0.1967 (6)	1.2795 (2)	0.2806 (2)	0.0302 (8)
H56	0.0693	1.2416	0.2980	0.036*
C57	0.3853 (6)	1.2574 (2)	0.2389 (2)	0.0264 (8)
H57	0.3864	1.2053	0.2264	0.032*
C58	0.5734 (6)	1.3121 (2)	0.2154 (2)	0.0234 (7)
H58	0.7063	1.2961	0.1886	0.028*
C59	0.5690 (6)	1.3899 (2)	0.2307 (2)	0.0212 (7)
H59	0.6982	1.4270	0.2134	0.025*
C61	−0.2773 (6)	1.8390 (2)	−0.0155 (2)	0.0241 (8)
H61A	−0.2662	1.7821	−0.0225	0.036*
H61B	−0.2750	1.8855	−0.0708	0.036*
H61C	−0.4257	1.8448	0.0126	0.036*
C62	−0.0668 (6)	1.8463 (2)	0.0380 (2)	0.0181 (7)
H62	0.0833	1.8338	0.0120	0.022*
C63	−0.0560 (6)	1.9360 (2)	0.0462 (2)	0.0202 (7)
H63A	−0.2022	1.9480	0.0734	0.024*
H63B	0.0807	1.9354	0.0831	0.024*
C64	−0.0316 (6)	2.0087 (2)	−0.0382 (2)	0.0187 (7)
C65	0.1685 (6)	2.0117 (2)	−0.0867 (3)	0.0257 (8)
H65	0.2927	1.9680	−0.0661	0.031*
C66	0.1908 (6)	2.0772 (2)	−0.1647 (3)	0.0265 (9)
H66	0.3303	2.0780	−0.1963	0.032*
C67	0.0122 (6)	2.1413 (2)	−0.1967 (3)	0.0222 (8)
H67	0.0275	2.1860	−0.2500	0.027*
C68	−0.1906 (6)	2.1390 (2)	−0.1493 (3)	0.0231 (8)
H68	−0.3157	2.1821	−0.1708	0.028*
C69	−0.2120 (6)	2.0741 (2)	−0.0708 (2)	0.0219 (8)
H69	−0.3504	2.0740	−0.0388	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0149 (4)	0.0286 (4)	0.0238 (4)	−0.0002 (3)	0.0020 (3)	−0.0123 (4)
Cl2	0.0184 (4)	0.0175 (4)	0.0292 (5)	−0.0041 (3)	−0.0007 (3)	−0.0042 (4)
Cl3	0.0159 (4)	0.0193 (4)	0.0221 (4)	−0.0018 (3)	0.0022 (3)	−0.0074 (3)
Cl4	0.0146 (3)	0.0194 (4)	0.0205 (4)	0.0010 (3)	−0.0025 (3)	−0.0038 (4)
Cl5	0.0218 (4)	0.0171 (4)	0.0239 (4)	−0.0034 (3)	0.0064 (3)	−0.0067 (4)
Cl6	0.0176 (4)	0.0209 (4)	0.0259 (4)	−0.0021 (3)	0.0013 (3)	−0.0065 (4)
N1	0.0214 (14)	0.0191 (14)	0.0227 (16)	0.0005 (11)	0.0057 (12)	−0.0092 (13)
N2	0.0184 (14)	0.0227 (15)	0.0293 (17)	−0.0036 (11)	0.0017 (12)	−0.0104 (13)
N3	0.0147 (13)	0.0219 (14)	0.0170 (14)	−0.0023 (11)	0.0035 (11)	−0.0075 (12)
N4	0.0147 (13)	0.0175 (14)	0.0252 (16)	−0.0031 (10)	−0.0018 (12)	−0.0083 (12)
N5	0.0137 (13)	0.0159 (13)	0.0195 (14)	−0.0023 (10)	−0.0036 (11)	−0.0028 (11)
N6	0.0137 (13)	0.0166 (13)	0.0226 (15)	0.0022 (10)	−0.0021 (11)	−0.0053 (12)
C1	0.032 (2)	0.028 (2)	0.034 (2)	−0.0059 (16)	0.0145 (18)	−0.0135 (18)
C2	0.0263 (18)	0.0133 (15)	0.0204 (18)	−0.0026 (13)	0.0025 (14)	−0.0047 (14)
C3	0.0308 (19)	0.0196 (17)	0.0169 (17)	0.0021 (14)	0.0065 (14)	−0.0055 (14)
C4	0.0230 (18)	0.0187 (17)	0.0184 (18)	−0.0029 (14)	0.0075 (15)	−0.0054 (14)
C5	0.0167 (16)	0.0210 (17)	0.0236 (19)	0.0006 (13)	0.0034 (14)	−0.0030 (15)
C6	0.0200 (17)	0.0263 (19)	0.0244 (19)	−0.0064 (14)	0.0043 (14)	−0.0094 (16)
C7	0.0276 (18)	0.0171 (17)	0.026 (2)	−0.0047 (14)	0.0118 (16)	−0.0115 (15)
C8	0.0225 (18)	0.0213 (18)	0.030 (2)	0.0026 (14)	0.0007 (16)	−0.0103 (16)
C9	0.0218 (17)	0.0197 (17)	0.0224 (19)	−0.0027 (14)	0.0014 (15)	−0.0067 (15)
C11	0.052 (3)	0.022 (2)	0.042 (3)	−0.0041 (18)	0.003 (2)	−0.0064 (19)
C12	0.0269 (19)	0.035 (2)	0.0187 (18)	−0.0052 (15)	−0.0022 (14)	−0.0008 (16)
C13	0.0233 (18)	0.036 (2)	0.028 (2)	−0.0033 (15)	0.0006 (15)	−0.0084 (17)
C14	0.0292 (19)	0.032 (2)	0.0250 (19)	−0.0063 (15)	0.0063 (15)	−0.0074 (16)
C15	0.050 (3)	0.045 (3)	0.039 (2)	−0.022 (2)	−0.018 (2)	0.001 (2)
C16	0.065 (3)	0.034 (2)	0.045 (3)	−0.024 (2)	−0.017 (2)	−0.004 (2)
C17	0.047 (2)	0.0264 (19)	0.029 (2)	0.0000 (16)	−0.0053 (17)	−0.0091 (16)
C18	0.036 (2)	0.0252 (19)	0.046 (2)	0.0041 (15)	−0.0166 (18)	−0.0090 (18)
C19	0.036 (2)	0.0243 (19)	0.044 (2)	−0.0054 (16)	−0.0046 (18)	−0.0087 (18)
C21	0.0243 (18)	0.0213 (18)	0.0258 (19)	−0.0052 (14)	0.0102 (15)	−0.0089 (15)
C22	0.0164 (15)	0.0149 (15)	0.0163 (16)	0.0003 (12)	0.0004 (13)	−0.0063 (13)
C23	0.0258 (17)	0.0212 (17)	0.0195 (18)	−0.0011 (13)	0.0060 (14)	−0.0052 (15)
C24	0.0252 (17)	0.0140 (15)	0.0161 (16)	−0.0050 (12)	0.0053 (14)	−0.0020 (13)
C25	0.0191 (17)	0.0233 (18)	0.035 (2)	0.0036 (14)	−0.0019 (16)	−0.0069 (17)
C26	0.0180 (17)	0.0275 (19)	0.034 (2)	−0.0032 (14)	−0.0056 (15)	−0.0077 (17)
C27	0.0261 (18)	0.0172 (17)	0.024 (2)	−0.0054 (14)	0.0044 (15)	−0.0044 (15)
C28	0.0272 (18)	0.0183 (17)	0.031 (2)	0.0024 (14)	−0.0023 (16)	−0.0065 (16)
C29	0.0214 (17)	0.0222 (17)	0.0235 (18)	0.0033 (13)	−0.0071 (15)	−0.0042 (15)
C31	0.0279 (19)	0.029 (2)	0.027 (2)	−0.0052 (16)	−0.0126 (16)	−0.0062 (17)
C32	0.0166 (15)	0.0174 (16)	0.0160 (16)	0.0004 (12)	−0.0020 (14)	−0.0034 (14)
C33	0.0229 (17)	0.0184 (17)	0.0240 (19)	0.0016 (13)	−0.0013 (14)	−0.0091 (14)
C34	0.0237 (17)	0.0141 (16)	0.0232 (19)	−0.0033 (13)	−0.0020 (15)	−0.0072 (15)
C35	0.0197 (17)	0.0196 (18)	0.031 (2)	0.0003 (14)	−0.0020 (15)	−0.0051 (16)
C36	0.0265 (19)	0.0261 (19)	0.031 (2)	−0.0034 (15)	0.0041 (16)	−0.0087 (17)
C37	0.0303 (19)	0.0176 (17)	0.024 (2)	−0.0077 (14)	0.0029 (16)	−0.0051 (15)
C38	0.0291 (19)	0.0161 (17)	0.029 (2)	0.0020 (14)	−0.0066 (16)	−0.0070 (15)
C39	0.0215 (17)	0.0181 (17)	0.0256 (19)	0.0027 (13)	0.0030 (14)	−0.0093 (15)
C51	0.0283 (18)	0.0178 (16)	0.0175 (17)	0.0020 (13)	−0.0015 (14)	−0.0030 (14)
C52	0.0154 (15)	0.0163 (15)	0.0186 (16)	0.0002 (12)	0.0015 (12)	−0.0060 (13)
C53	0.0213 (16)	0.0190 (16)	0.0238 (18)	0.0003 (12)	−0.0024 (13)	−0.0089 (14)
C54	0.0198 (16)	0.0241 (17)	0.0138 (15)	0.0016 (13)	−0.0068 (13)	−0.0044 (13)
C55	0.0155 (16)	0.030 (2)	0.038 (2)	0.0026 (14)	−0.0013 (15)	−0.0166 (17)
C56	0.0223 (18)	0.0277 (19)	0.043 (2)	−0.0042 (14)	−0.0064 (16)	−0.0151 (18)
C57	0.0308 (19)	0.0200 (17)	0.030 (2)	0.0026 (14)	−0.0103 (16)	−0.0118 (15)
C58	0.0292 (17)	0.0209 (16)	0.0196 (17)	0.0050 (13)	−0.0034 (14)	−0.0074 (14)
C59	0.0231 (16)	0.0242 (17)	0.0160 (16)	−0.0005 (13)	−0.0016 (13)	−0.0067 (14)
C61	0.0254 (18)	0.0212 (18)	0.0227 (19)	−0.0039 (14)	−0.0039 (15)	−0.0038 (15)
C62	0.0202 (16)	0.0149 (16)	0.0173 (17)	0.0004 (12)	−0.0047 (14)	−0.0033 (13)
C63	0.0266 (18)	0.0129 (16)	0.0189 (17)	0.0009 (13)	−0.0033 (14)	−0.0032 (13)
C64	0.0205 (16)	0.0107 (15)	0.0245 (19)	0.0004 (12)	−0.0031 (15)	−0.0056 (14)
C65	0.0183 (17)	0.0172 (17)	0.036 (2)	0.0031 (13)	−0.0027 (16)	−0.0028 (16)
C66	0.0209 (18)	0.0183 (18)	0.039 (2)	−0.0041 (13)	0.0080 (16)	−0.0077 (16)
C67	0.0259 (19)	0.0143 (17)	0.024 (2)	−0.0054 (13)	0.0019 (15)	−0.0033 (15)
C68	0.0200 (17)	0.0156 (17)	0.030 (2)	0.0054 (13)	−0.0030 (15)	−0.0048 (15)
C69	0.0218 (17)	0.0144 (16)	0.030 (2)	−0.0026 (13)	0.0062 (15)	−0.0081 (15)

Geometric parameters (Å, º)

N1—C2	1.515 (4)	C23—H23B	0.9900
N1—H1A	0.9100	C24—C29	1.385 (5)
N1—H1B	0.9100	C24—C25	1.403 (5)
N1—H1C	0.9100	C25—C26	1.374 (5)
N2—C12	1.531 (5)	C25—H25	0.9500
N2—H2A	0.9100	C26—C27	1.391 (5)
N2—H2B	0.9100	C26—H26	0.9500
N2—H2C	0.9100	C27—C28	1.385 (5)
N3—C22	1.494 (4)	C27—H27	0.9500
N3—H3A	0.9100	C28—C29	1.403 (5)
N3—H3B	0.9100	C28—H28	0.9500
N3—H3C	0.9100	C29—H29	0.9500
N4—C32	1.497 (4)	C31—C32	1.537 (5)
N4—H4A	0.9100	C31—H31A	0.9800
N4—H4B	0.9100	C31—H31B	0.9800
N4—H4C	0.9100	C31—H31C	0.9800
N5—C52	1.508 (4)	C32—C33	1.525 (4)
N5—H5A	0.9100	C32—H32	1.0000
N5—H5B	0.9100	C33—C34	1.511 (5)
N5—H5C	0.9100	C33—H33A	0.9900
N6—C62	1.495 (4)	C33—H33B	0.9900
N6—H6A	0.9100	C34—C35	1.394 (5)
N6—H6B	0.9100	C34—C39	1.395 (5)
N6—H6C	0.9100	C35—C36	1.385 (5)
C1—C2	1.505 (5)	C35—H35	0.9500
C1—H1D	0.9800	C36—C37	1.395 (5)
C1—H1E	0.9800	C36—H36	0.9500
C1—H1F	0.9800	C37—C38	1.389 (5)
C2—C3	1.537 (4)	C37—H37	0.9500
C2—H2	1.0000	C38—C39	1.397 (5)
C3—C4	1.514 (5)	C38—H38	0.9500
C3—H3D	0.9900	C39—H39	0.9500
C3—H3E	0.9900	C51—C52	1.534 (4)
C4—C5	1.390 (5)	C51—H51A	0.9800
C4—C9	1.404 (5)	C51—H51B	0.9800
C5—C6	1.391 (5)	C51—H51C	0.9800
C5—H5	0.9500	C52—C53	1.539 (4)
C6—C7	1.394 (5)	C52—H52	1.0000
C6—H6	0.9500	C53—C54	1.511 (5)
C7—C8	1.378 (6)	C53—H53A	0.9900
C7—H7	0.9500	C53—H53B	0.9900
C8—C9	1.382 (5)	C54—C59	1.401 (5)
C8—H8	0.9500	C54—C55	1.408 (5)
C9—H9	0.9500	C55—C56	1.397 (5)
C11—C12	1.504 (5)	C55—H55	0.9500
C11—H11A	0.9800	C56—C57	1.381 (5)
C11—H11B	0.9800	C56—H56	0.9500
C11—H11C	0.9800	C57—C58	1.388 (5)
C12—C13	1.521 (5)	C57—H57	0.9500
C12—H12	1.0000	C58—C59	1.388 (5)
C13—C14	1.543 (5)	C58—H58	0.9500
C13—H13A	0.9900	C59—H59	0.9500
C13—H13B	0.9900	C61—C62	1.528 (5)
C14—C15	1.385 (5)	C61—H61A	0.9800
C14—C19	1.393 (5)	C61—H61B	0.9800
C15—C16	1.370 (6)	C61—H61C	0.9800
C15—H15	0.9500	C62—C63	1.529 (4)
C16—C17	1.374 (6)	C62—H62	1.0000
C16—H16	0.9500	C63—C64	1.518 (5)
C17—C18	1.369 (5)	C63—H63A	0.9900
C17—H17	0.9500	C63—H63B	0.9900
C18—C19	1.380 (5)	C64—C65	1.389 (5)
C18—H18	0.9500	C64—C69	1.403 (5)
C19—H19	0.9500	C65—C66	1.391 (5)
C21—C22	1.511 (5)	C65—H65	0.9500
C21—H21A	0.9800	C66—C67	1.382 (5)
C21—H21B	0.9800	C66—H66	0.9500
C21—H21C	0.9800	C67—C68	1.392 (5)
C22—C23	1.542 (4)	C67—H67	0.9500
C22—H22	1.0000	C68—C69	1.392 (5)
C23—C24	1.505 (5)	C68—H68	0.9500
C23—H23A	0.9900	C69—H69	0.9500
C2—N1—H1A	109.5	C29—C24—C25	116.9 (3)
C2—N1—H1B	109.5	C29—C24—C23	121.3 (3)
H1A—N1—H1B	109.5	C25—C24—C23	121.8 (3)
C2—N1—H1C	109.5	C26—C25—C24	122.3 (3)
H1A—N1—H1C	109.5	C26—C25—H25	118.8
H1B—N1—H1C	109.5	C24—C25—H25	118.8
C12—N2—H2A	109.5	C25—C26—C27	119.9 (3)
C12—N2—H2B	109.5	C25—C26—H26	120.0
H2A—N2—H2B	109.5	C27—C26—H26	120.0
C12—N2—H2C	109.5	C28—C27—C26	119.4 (4)
H2A—N2—H2C	109.5	C28—C27—H27	120.3
H2B—N2—H2C	109.5	C26—C27—H27	120.3
C22—N3—H3A	109.5	C27—C28—C29	119.8 (3)
C22—N3—H3B	109.5	C27—C28—H28	120.1
H3A—N3—H3B	109.5	C29—C28—H28	120.1
C22—N3—H3C	109.5	C24—C29—C28	121.7 (3)
H3A—N3—H3C	109.5	C24—C29—H29	119.2
H3B—N3—H3C	109.5	C28—C29—H29	119.2
C32—N4—H4A	109.5	C32—C31—H31A	109.5
C32—N4—H4B	109.5	C32—C31—H31B	109.5
H4A—N4—H4B	109.5	H31A—C31—H31B	109.5
C32—N4—H4C	109.5	C32—C31—H31C	109.5
H4A—N4—H4C	109.5	H31A—C31—H31C	109.5
H4B—N4—H4C	109.5	H31B—C31—H31C	109.5
C52—N5—H5A	109.5	N4—C32—C33	110.3 (3)
C52—N5—H5B	109.5	N4—C32—C31	107.9 (3)
H5A—N5—H5B	109.5	C33—C32—C31	113.3 (3)
C52—N5—H5C	109.5	N4—C32—H32	108.4
H5A—N5—H5C	109.5	C33—C32—H32	108.4
H5B—N5—H5C	109.5	C31—C32—H32	108.4
C62—N6—H6A	109.5	C34—C33—C32	111.7 (3)
C62—N6—H6B	109.5	C34—C33—H33A	109.3
H6A—N6—H6B	109.5	C32—C33—H33A	109.3
C62—N6—H6C	109.5	C34—C33—H33B	109.3
H6A—N6—H6C	109.5	C32—C33—H33B	109.3
H6B—N6—H6C	109.5	H33A—C33—H33B	107.9
C2—C1—H1D	109.5	C35—C34—C39	117.8 (3)
C2—C1—H1E	109.5	C35—C34—C33	120.8 (3)
H1D—C1—H1E	109.5	C39—C34—C33	121.2 (3)
C2—C1—H1F	109.5	C36—C35—C34	121.1 (3)
H1D—C1—H1F	109.5	C36—C35—H35	119.4
H1E—C1—H1F	109.5	C34—C35—H35	119.4
C1—C2—N1	107.8 (3)	C35—C36—C37	120.6 (3)
C1—C2—C3	114.1 (3)	C35—C36—H36	119.7
N1—C2—C3	108.1 (3)	C37—C36—H36	119.7
C1—C2—H2	108.9	C38—C37—C36	119.1 (4)
N1—C2—H2	108.9	C38—C37—H37	120.4
C3—C2—H2	108.9	C36—C37—H37	120.4
C4—C3—C2	112.0 (3)	C37—C38—C39	119.8 (3)
C4—C3—H3D	109.2	C37—C38—H38	120.1
C2—C3—H3D	109.2	C39—C38—H38	120.1
C4—C3—H3E	109.2	C34—C39—C38	121.5 (3)
C2—C3—H3E	109.2	C34—C39—H39	119.3
H3D—C3—H3E	107.9	C38—C39—H39	119.3
C5—C4—C9	118.6 (3)	C52—C51—H51A	109.5
C5—C4—C3	121.1 (3)	C52—C51—H51B	109.5
C9—C4—C3	120.2 (3)	H51A—C51—H51B	109.5
C4—C5—C6	120.5 (3)	C52—C51—H51C	109.5
C4—C5—H5	119.7	H51A—C51—H51C	109.5
C6—C5—H5	119.7	H51B—C51—H51C	109.5
C5—C6—C7	120.4 (3)	N5—C52—C51	107.9 (3)
C5—C6—H6	119.8	N5—C52—C53	108.6 (2)
C7—C6—H6	119.8	C51—C52—C53	113.5 (3)
C8—C7—C6	119.2 (4)	N5—C52—H52	108.9
C8—C7—H7	120.4	C51—C52—H52	108.9
C6—C7—H7	120.4	C53—C52—H52	108.9
C7—C8—C9	120.9 (3)	C54—C53—C52	112.6 (3)
C7—C8—H8	119.6	C54—C53—H53A	109.1
C9—C8—H8	119.6	C52—C53—H53A	109.1
C8—C9—C4	120.5 (3)	C54—C53—H53B	109.1
C8—C9—H9	119.8	C52—C53—H53B	109.1
C4—C9—H9	119.8	H53A—C53—H53B	107.8
C12—C11—H11A	109.5	C59—C54—C55	117.7 (3)
C12—C11—H11B	109.5	C59—C54—C53	121.9 (3)
H11A—C11—H11B	109.5	C55—C54—C53	120.4 (3)
C12—C11—H11C	109.5	C56—C55—C54	120.6 (3)
H11A—C11—H11C	109.5	C56—C55—H55	119.7
H11B—C11—H11C	109.5	C54—C55—H55	119.7
C11—C12—C13	113.4 (3)	C57—C56—C55	120.6 (3)
C11—C12—N2	109.1 (3)	C57—C56—H56	119.7
C13—C12—N2	110.1 (3)	C55—C56—H56	119.7
C11—C12—H12	108.0	C56—C57—C58	119.4 (3)
C13—C12—H12	108.0	C56—C57—H57	120.3
N2—C12—H12	108.0	C58—C57—H57	120.3
C12—C13—C14	110.6 (3)	C59—C58—C57	120.6 (3)
C12—C13—H13A	109.5	C59—C58—H58	119.7
C14—C13—H13A	109.5	C57—C58—H58	119.7
C12—C13—H13B	109.5	C58—C59—C54	121.1 (3)
C14—C13—H13B	109.5	C58—C59—H59	119.5
H13A—C13—H13B	108.1	C54—C59—H59	119.5
C15—C14—C19	118.5 (4)	C62—C61—H61A	109.5
C15—C14—C13	121.3 (4)	C62—C61—H61B	109.5
C19—C14—C13	120.2 (3)	H61A—C61—H61B	109.5
C16—C15—C14	120.3 (4)	C62—C61—H61C	109.5
C16—C15—H15	119.9	H61A—C61—H61C	109.5
C14—C15—H15	119.9	H61B—C61—H61C	109.5
C15—C16—C17	121.0 (4)	N6—C62—C61	108.3 (3)
C15—C16—H16	119.5	N6—C62—C63	108.9 (3)
C17—C16—H16	119.5	C61—C62—C63	113.5 (3)
C18—C17—C16	119.5 (4)	N6—C62—H62	108.7
C18—C17—H17	120.2	C61—C62—H62	108.7
C16—C17—H17	120.2	C63—C62—H62	108.7
C17—C18—C19	120.1 (4)	C64—C63—C62	112.7 (3)
C17—C18—H18	120.0	C64—C63—H63A	109.1
C19—C18—H18	120.0	C62—C63—H63A	109.1
C18—C19—C14	120.6 (4)	C64—C63—H63B	109.1
C18—C19—H19	119.7	C62—C63—H63B	109.1
C14—C19—H19	119.7	H63A—C63—H63B	107.8
C22—C21—H21A	109.5	C65—C64—C69	117.7 (3)
C22—C21—H21B	109.5	C65—C64—C63	121.0 (3)
H21A—C21—H21B	109.5	C69—C64—C63	121.3 (3)
C22—C21—H21C	109.5	C64—C65—C66	121.4 (3)
H21A—C21—H21C	109.5	C64—C65—H65	119.3
H21B—C21—H21C	109.5	C66—C65—H65	119.3
N3—C22—C21	108.4 (3)	C67—C66—C65	120.7 (4)
N3—C22—C23	109.1 (3)	C67—C66—H66	119.7
C21—C22—C23	113.6 (3)	C65—C66—H66	119.7
N3—C22—H22	108.5	C66—C67—C68	118.7 (4)
C21—C22—H22	108.5	C66—C67—H67	120.6
C23—C22—H22	108.5	C68—C67—H67	120.6
C24—C23—C22	112.2 (3)	C69—C68—C67	120.7 (3)
C24—C23—H23A	109.2	C69—C68—H68	119.7
C22—C23—H23A	109.2	C67—C68—H68	119.7
C24—C23—H23B	109.2	C68—C69—C64	120.8 (3)
C22—C23—H23B	109.2	C68—C69—H69	119.6
H23A—C23—H23B	107.9	C64—C69—H69	119.6
C1—C2—C3—C4	−57.2 (4)	N4—C32—C33—C34	−179.0 (3)
N1—C2—C3—C4	−177.0 (3)	C31—C32—C33—C34	−57.9 (4)
C2—C3—C4—C5	−69.3 (4)	C32—C33—C34—C35	−66.7 (4)
C2—C3—C4—C9	106.9 (4)	C32—C33—C34—C39	109.7 (4)
C9—C4—C5—C6	1.0 (5)	C39—C34—C35—C36	0.1 (5)
C3—C4—C5—C6	177.3 (3)	C33—C34—C35—C36	176.6 (3)
C4—C5—C6—C7	−0.4 (5)	C34—C35—C36—C37	−0.8 (6)
C5—C6—C7—C8	0.1 (6)	C35—C36—C37—C38	0.7 (6)
C6—C7—C8—C9	−0.5 (6)	C36—C37—C38—C39	0.1 (5)
C7—C8—C9—C4	1.2 (6)	C35—C34—C39—C38	0.7 (5)
C5—C4—C9—C8	−1.4 (5)	C33—C34—C39—C38	−175.8 (3)
C3—C4—C9—C8	−177.7 (3)	C37—C38—C39—C34	−0.8 (5)
C11—C12—C13—C14	−60.7 (4)	N5—C52—C53—C54	179.3 (3)
N2—C12—C13—C14	176.7 (3)	C51—C52—C53—C54	−60.8 (4)
C12—C13—C14—C15	115.4 (4)	C52—C53—C54—C59	−52.7 (4)
C12—C13—C14—C19	−61.9 (5)	C52—C53—C54—C55	127.5 (3)
C19—C14—C15—C16	−0.4 (7)	C59—C54—C55—C56	−2.2 (5)
C13—C14—C15—C16	−177.8 (5)	C53—C54—C55—C56	177.6 (3)
C14—C15—C16—C17	0.1 (8)	C54—C55—C56—C57	0.8 (6)
C15—C16—C17—C18	1.6 (8)	C55—C56—C57—C58	1.5 (6)
C16—C17—C18—C19	−3.0 (7)	C56—C57—C58—C59	−2.4 (5)
C17—C18—C19—C14	2.8 (7)	C57—C58—C59—C54	1.0 (5)
C15—C14—C19—C18	−1.1 (6)	C55—C54—C59—C58	1.3 (5)
C13—C14—C19—C18	176.3 (4)	C53—C54—C59—C58	−178.5 (3)
N3—C22—C23—C24	177.6 (3)	N6—C62—C63—C64	178.6 (3)
C21—C22—C23—C24	−61.3 (4)	C61—C62—C63—C64	−60.7 (4)
C22—C23—C24—C29	113.2 (4)	C62—C63—C64—C65	−63.9 (4)
C22—C23—C24—C25	−65.1 (4)	C62—C63—C64—C69	114.7 (4)
C29—C24—C25—C26	0.2 (5)	C69—C64—C65—C66	0.3 (5)
C23—C24—C25—C26	178.6 (3)	C63—C64—C65—C66	179.0 (3)
C24—C25—C26—C27	−0.7 (6)	C64—C65—C66—C67	−0.6 (6)
C25—C26—C27—C28	0.3 (6)	C65—C66—C67—C68	0.1 (6)
C26—C27—C28—C29	0.6 (5)	C66—C67—C68—C69	0.8 (6)
C25—C24—C29—C28	0.7 (5)	C67—C68—C69—C64	−1.1 (6)
C23—C24—C29—C28	−177.7 (3)	C65—C64—C69—C68	0.5 (5)
C27—C28—C29—C24	−1.1 (6)	C63—C64—C69—C68	−178.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl5^i	0.91	2.40	3.304 (3)	171
N1—H1B···Cl5^ii	0.91	2.27	3.177 (3)	171
N1—H1C···Cl6^i	0.91	2.28	3.181 (3)	169
N2—H2A···Cl6^iii	0.91	2.27	3.179 (3)	174
N2—H2B···Cl1^iv	0.91	2.43	3.215 (3)	145
N2—H2C···Cl6^i	0.91	2.37	3.233 (3)	158
N3—H3A···Cl1^iv	0.91	2.28	3.151 (3)	159
N3—H3B···Cl1	0.91	2.22	3.118 (3)	168
N3—H3C···Cl2	0.91	2.27	3.171 (3)	169
N4—H4A···Cl2	0.91	2.25	3.149 (3)	168
N4—H4B···Cl3	0.91	2.26	3.164 (3)	172
N4—H4C···Cl2^v	0.91	2.37	3.271 (3)	171
N5—H5A···Cl3	0.91	2.27	3.159 (3)	165
N5—H5B···Cl4	0.91	2.36	3.196 (3)	153
N5—H5C···Cl3^iv	0.91	2.33	3.233 (3)	170
N6—H6A···Cl4	0.91	2.22	3.117 (3)	167
N6—H6B···Cl5^v	0.91	2.27	3.168 (3)	169
N6—H6C···Cl4^v	0.91	2.29	3.158 (3)	161

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

(II) (2S)-1-Phenylpropan-2-aminium bromide

Crystal data

C9H14N^+·Br^−	F(000) = 220
Mr = 216.12	Dx = 1.432 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2yb	Cell parameters from 5999 reflections
a = 5.2366 (4) Å	θ = 3.0–27.5°
b = 8.4264 (5) Å	µ = 4.04 mm^−1
c = 11.3895 (8) Å	T = 100 K
β = 94.079 (2)°	Blade, colourless
V = 501.30 (6) Å^3	0.25 × 0.18 × 0.12 mm
Z = 2

Data collection

Rigaku Saturn724+ (2x2 bin mode) diffractometer	2383 independent reflections
Radiation source: fine-focus sealed tube	2343 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 28.5714 pixels mm^-1	θmax = 30.1°, θmin = 3.0°
profile data from ω scans	h = −7→7
Absorption correction: multi-scan (CrystalClear-SM Expert; Rigaku, 2012)	k = −11→10
Tmin = 0.711, Tmax = 1.000	l = −16→15
5432 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.020	w = 1/[σ^2(Fo^2) + (0.0329P)^2 + 0.1173P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.052	(Δ/σ)max = 0.001
S = 1.08	Δρmax = 0.29 e Å^−3
2383 reflections	Δρmin = −0.39 e Å^−3
115 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.045 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with 962 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.003 (10)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Br1	0.08467 (3)	0.71309 (4)	0.418045 (13)	0.02270 (7)
N1	0.6129 (4)	0.5569 (2)	0.55110 (15)	0.0206 (3)
C1	0.6190 (5)	0.7824 (3)	0.6887 (2)	0.0267 (5)
H1A	0.7315	0.8410	0.6389	0.040*
H1B	0.6541	0.8148	0.7709	0.040*
H1C	0.4400	0.8055	0.6636	0.040*
C2	0.6679 (4)	0.6056 (3)	0.67731 (19)	0.0198 (4)
H2	0.8533	0.5854	0.6994	0.024*
C3	0.5097 (3)	0.5028 (2)	0.75640 (17)	0.0202 (4)
H3A	0.3326	0.5442	0.7546	0.024*
H3B	0.5024	0.3927	0.7260	0.024*
C4	0.6258 (3)	0.5028 (2)	0.88157 (17)	0.0187 (3)
C5	0.8463 (4)	0.4144 (2)	0.91057 (17)	0.0209 (4)
H5	0.9208	0.3539	0.8514	0.025*
C6	0.9585 (4)	0.4134 (3)	1.02495 (18)	0.0237 (4)
H6	1.1085	0.3524	1.0435	0.028*
C7	0.8511 (4)	0.5017 (3)	1.11225 (19)	0.0262 (4)
H7	0.9281	0.5019	1.1903	0.031*
C8	0.6311 (4)	0.5894 (3)	1.08438 (19)	0.0269 (4)
H8	0.5567	0.6492	1.1439	0.032*
C9	0.5187 (4)	0.5905 (3)	0.97025 (18)	0.0240 (4)
H9	0.3680	0.6511	0.9522	0.029*
H1N	0.649 (5)	0.461 (4)	0.542 (2)	0.030 (7)*
H2N	0.724 (5)	0.604 (4)	0.501 (3)	0.033 (7)*
H3N	0.442 (6)	0.576 (4)	0.524 (3)	0.038 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.02399 (10)	0.02052 (10)	0.02300 (10)	−0.00361 (9)	−0.00246 (6)	0.00244 (9)
N1	0.0249 (8)	0.0182 (8)	0.0183 (7)	0.0019 (6)	−0.0017 (6)	0.0003 (6)
C1	0.0379 (14)	0.0202 (11)	0.0209 (10)	−0.0013 (9)	−0.0059 (9)	−0.0007 (8)
C2	0.0210 (9)	0.0203 (10)	0.0174 (9)	−0.0024 (8)	−0.0029 (7)	0.0023 (8)
C3	0.0175 (8)	0.0216 (9)	0.0210 (8)	−0.0022 (7)	−0.0029 (6)	0.0018 (7)
C4	0.0185 (8)	0.0185 (9)	0.0191 (8)	−0.0040 (7)	0.0015 (6)	0.0013 (7)
C5	0.0217 (9)	0.0221 (9)	0.0190 (8)	0.0006 (7)	0.0018 (7)	0.0017 (7)
C6	0.0218 (9)	0.0271 (10)	0.0218 (9)	−0.0007 (7)	−0.0021 (7)	0.0038 (7)
C7	0.0318 (10)	0.0258 (10)	0.0204 (8)	−0.0069 (8)	−0.0030 (8)	0.0029 (8)
C8	0.0374 (11)	0.0222 (10)	0.0217 (9)	−0.0001 (8)	0.0055 (8)	−0.0024 (8)
C9	0.0257 (9)	0.0206 (9)	0.0258 (10)	0.0035 (7)	0.0029 (8)	0.0015 (8)

Geometric parameters (Å, º)

N1—C2	1.503 (3)	C3—H3B	0.9900
N1—H1N	0.83 (3)	C4—C5	1.394 (3)
N1—H2N	0.93 (3)	C4—C9	1.400 (3)
N1—H3N	0.94 (3)	C5—C6	1.391 (3)
C1—C2	1.519 (3)	C5—H5	0.9500
C1—H1A	0.9800	C6—C7	1.392 (3)
C1—H1B	0.9800	C6—H6	0.9500
C1—H1C	0.9800	C7—C8	1.386 (3)
C2—C3	1.534 (3)	C7—H7	0.9500
C2—H2	1.0000	C8—C9	1.388 (3)
C3—C4	1.509 (3)	C8—H8	0.9500
C3—H3A	0.9900	C9—H9	0.9500
C2—N1—H1N	110.3 (19)	C4—C3—H3B	109.5
C2—N1—H2N	112.5 (18)	C2—C3—H3B	109.5
H1N—N1—H2N	100 (2)	H3A—C3—H3B	108.1
C2—N1—H3N	112.6 (19)	C5—C4—C9	118.60 (18)
H1N—N1—H3N	110 (3)	C5—C4—C3	119.65 (18)
H2N—N1—H3N	111 (3)	C9—C4—C3	121.76 (18)
C2—C1—H1A	109.5	C6—C5—C4	120.84 (18)
C2—C1—H1B	109.5	C6—C5—H5	119.6
H1A—C1—H1B	109.5	C4—C5—H5	119.6
C2—C1—H1C	109.5	C5—C6—C7	120.05 (19)
H1A—C1—H1C	109.5	C5—C6—H6	120.0
H1B—C1—H1C	109.5	C7—C6—H6	120.0
N1—C2—C1	109.1 (2)	C8—C7—C6	119.52 (19)
N1—C2—C3	109.44 (17)	C8—C7—H7	120.2
C1—C2—C3	113.74 (19)	C6—C7—H7	120.2
N1—C2—H2	108.1	C7—C8—C9	120.5 (2)
C1—C2—H2	108.1	C7—C8—H8	119.7
C3—C2—H2	108.1	C9—C8—H8	119.7
C4—C3—C2	110.88 (16)	C8—C9—C4	120.46 (19)
C4—C3—H3A	109.5	C8—C9—H9	119.8
C2—C3—H3A	109.5	C4—C9—H9	119.8
N1—C2—C3—C4	158.84 (17)	C4—C5—C6—C7	−0.1 (3)
C1—C2—C3—C4	−78.9 (2)	C5—C6—C7—C8	0.5 (3)
C2—C3—C4—C5	−75.2 (2)	C6—C7—C8—C9	−0.4 (3)
C2—C3—C4—C9	104.5 (2)	C7—C8—C9—C4	0.1 (3)
C9—C4—C5—C6	−0.3 (3)	C5—C4—C9—C8	0.3 (3)
C3—C4—C5—C6	179.42 (19)	C3—C4—C9—C8	−179.38 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Br1^i	0.83 (3)	2.54 (3)	3.3080 (19)	154 (2)
N1—H2N···Br1^ii	0.93 (3)	2.36 (3)	3.2656 (19)	165 (3)
N1—H3N···Br1	0.94 (3)	2.44 (3)	3.3296 (18)	157 (3)

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