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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615015867/fm3034sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015867/fm3034Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015867/fm3034IIsup3.hkl
Contains datablock II

CCDC references: 1420443; 1420442

Introduction top

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.

Experimental top

Synthesis and crystallization top

(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.

Refinement top

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 Uiso(H) = 1.5Ueq(C) for methyl groups and 1.2Ueq(C) otherwise. In (I), the H atoms of the NH3 groups were similarly modelled, with N—H = 0.91 Å and Uiso(H) = 1.5Ueq(N). However, for (II), H atoms bound to N were refined isotropically (see Tables 3 and 4).

Results and discussion top

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 ππ 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 top

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 top
[Figure 1] Fig. 1. The molecular structure of hydrochloride salt (I), with the non-H atoms shown as 50% probability displacement ellipsoids.
[Figure 2] 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.
[Figure 3] Fig. 3. The molecular structure of hydrobromide salt (II), with the non-H atoms shown as 50% probability displacement ellipsoids.
[Figure 4] 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.
[Figure 5] 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 top
Crystal data top
C9H14N+·ClZ = 6
Mr = 171.66F(000) = 552
Triclinic, P1Dx = 1.167 Mg m3
Hall symbol: P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.6396 (4) ÅCell parameters from 24532 reflections
b = 16.3917 (11) Åθ = 2.1–27.5°
c = 16.9602 (12) ŵ = 0.33 mm1
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) Å3
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
19328 independent reflections
Radiation source: fine-focus sealed tube17180 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.0000
Detector resolution: 28.5714 pixels mm-1θmax = 29.8°, θmin = 1.5°
profile data from ω–scansh = 77
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2012)
k = 2222
Tmin = 0.593, Tmax = 1.000l = 2322
19328 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.129 w = 1/[σ2(Fo2) + (0.070P)2 + 0.9426P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.001
19328 reflectionsΔρmax = 0.60 e Å3
608 parametersΔρmin = 0.31 e Å3
3 restraintsAbsolute structure: Flack (1983), with 7328 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.01 (4)
Crystal data top
C9H14N+·Clγ = 87.286 (5)°
Mr = 171.66V = 1465.98 (18) Å3
Triclinic, P1Z = 6
a = 5.6396 (4) ÅMo Kα radiation
b = 16.3917 (11) ŵ = 0.33 mm1
c = 16.9602 (12) ÅT = 100 K
α = 69.427 (4)°0.18 × 0.06 × 0.01 mm
β = 89.995 (5)°
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
19328 independent reflections
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2012)
17180 reflections with I > 2σ(I)
Tmin = 0.593, Tmax = 1.000Rint = 0.0000
19328 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.129Δρmax = 0.60 e Å3
S = 1.03Δρmin = 0.31 e Å3
19328 reflectionsAbsolute structure: Flack (1983), with 7328 Friedel pairs
608 parametersAbsolute structure parameter: 0.01 (4)
3 restraints
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cl10.06769 (12)1.62848 (5)0.75422 (6)0.02168 (17)
Cl20.53180 (13)1.80851 (5)0.53529 (6)0.02264 (18)
Cl30.06999 (12)1.61130 (5)0.42734 (5)0.01902 (16)
Cl40.41074 (12)1.78429 (5)0.20307 (5)0.01911 (16)
Cl50.80481 (13)1.59774 (5)0.10755 (5)0.02096 (17)
Cl60.27312 (12)1.80318 (5)0.14216 (5)0.02188 (17)
N10.2889 (5)1.61990 (18)1.00800 (18)0.0206 (6)
H1A0.42371.60911.04030.031*
H1B0.16001.61251.04170.031*
H1C0.28501.67570.97080.031*
N20.7768 (5)1.81575 (18)0.76431 (19)0.0231 (6)
H2A0.91741.81620.79050.035*
H2B0.78791.77520.73900.035*
H2C0.65961.80230.80300.035*
N30.4294 (5)1.62596 (18)0.67440 (17)0.0176 (6)
H3A0.55991.61480.70880.026*
H3B0.29641.62460.70510.026*
H3C0.43721.67960.63380.026*
N40.0460 (5)1.79490 (17)0.45030 (18)0.0189 (6)
H4A0.17291.80160.48030.028*
H4B0.05231.73980.44910.028*
H4C0.09061.80430.47510.028*
N50.5642 (5)1.60012 (17)0.34301 (17)0.0172 (6)
H5A0.43781.60040.37630.026*
H5B0.54031.64310.29190.026*
H5C0.69841.60950.36770.026*
N60.0844 (5)1.77880 (17)0.12398 (17)0.0182 (6)
H6A0.04711.77870.15510.027*
H6B0.09511.72530.11960.027*
H6C0.21581.79130.14960.027*
C10.5080 (7)1.5677 (3)0.9095 (3)0.0304 (9)
H1D0.51371.62830.87100.046*
H1E0.50851.52880.87700.046*
H1F0.64691.55290.94760.046*
C20.2852 (6)1.5573 (2)0.9602 (2)0.0203 (7)
H20.14461.57330.92090.024*
C30.2596 (6)1.4649 (2)1.0243 (2)0.0228 (7)
H3D0.38951.45111.06700.027*
H3E0.10721.46281.05380.027*
C40.2671 (6)1.3968 (2)0.9828 (2)0.0203 (7)
C50.0827 (6)1.3923 (2)0.9303 (2)0.0218 (7)
H50.05371.43090.92200.026*
C60.0963 (6)1.3318 (2)0.8898 (2)0.0233 (8)
H60.03111.32900.85430.028*
C70.2959 (6)1.2751 (2)0.9009 (3)0.0226 (8)
H70.30541.23380.87320.027*
C80.4794 (7)1.2797 (2)0.9526 (2)0.0244 (8)
H80.61531.24100.96080.029*
C90.4681 (6)1.3400 (2)0.9928 (2)0.0215 (8)
H90.59741.34301.02740.026*
C110.6831 (8)1.9714 (3)0.7410 (3)0.0401 (10)
H11A0.83071.97470.77000.060*
H11B0.55621.95350.78210.060*
H11C0.63922.02880.69900.060*
C120.7190 (7)1.9059 (3)0.6978 (2)0.0289 (8)
H120.56611.90340.66910.035*
C130.9113 (7)1.9288 (3)0.6319 (2)0.0299 (8)
H13A0.92931.88260.60700.036*
H13B1.06461.93190.65890.036*
C140.8476 (7)2.0172 (2)0.5618 (2)0.0292 (8)
C150.9846 (8)2.0886 (3)0.5489 (3)0.0479 (12)
H151.12392.08300.58220.057*
C160.9201 (9)2.1672 (3)0.4881 (3)0.0502 (13)
H161.01562.21560.47980.060*
C170.7193 (7)2.1771 (3)0.4391 (2)0.0342 (9)
H170.67852.23150.39620.041*
C180.5783 (7)2.1078 (2)0.4525 (3)0.0368 (9)
H180.43522.11500.42070.044*
C190.6437 (7)2.0277 (2)0.5121 (3)0.0356 (9)
H190.54891.97930.51940.043*
C210.6330 (6)1.5667 (2)0.5781 (2)0.0235 (8)
H21A0.62391.62410.53310.035*
H21B0.63401.52100.55320.035*
H21C0.77891.56040.61150.035*
C220.4206 (6)1.5584 (2)0.6341 (2)0.0157 (6)
H220.27321.57020.59830.019*
C230.4086 (6)1.4677 (2)0.7034 (2)0.0227 (7)
H23A0.55301.45570.73960.027*
H23B0.26971.46780.73900.027*
C240.3889 (6)1.3964 (2)0.6675 (2)0.0192 (7)
C250.1894 (6)1.3917 (2)0.6201 (3)0.0270 (8)
H250.06201.43410.61170.032*
C260.1718 (6)1.3279 (2)0.5856 (2)0.0272 (8)
H260.03321.32630.55440.033*
C270.3570 (6)1.2656 (2)0.5963 (2)0.0230 (8)
H270.34611.22150.57230.028*
C280.5574 (6)1.2685 (2)0.6422 (2)0.0261 (8)
H280.68561.22660.64950.031*
C290.5706 (6)1.3334 (2)0.6780 (2)0.0235 (7)
H290.70771.33420.71020.028*
C310.1718 (7)1.8495 (2)0.3151 (2)0.0286 (9)
H31A0.17361.78970.31510.043*
H31B0.17101.89050.25690.043*
H31C0.31331.86200.34320.043*
C320.0519 (6)1.8592 (2)0.3622 (2)0.0173 (7)
H320.19421.84400.33400.021*
C330.0743 (6)1.9512 (2)0.3631 (2)0.0214 (7)
H33A0.06041.96570.39410.026*
H33B0.22281.95330.39330.026*
C340.0766 (6)2.0180 (2)0.2751 (2)0.0201 (7)
C350.2649 (6)2.0187 (2)0.2217 (2)0.0243 (8)
H350.39731.97860.24200.029*
C360.2624 (7)2.0769 (2)0.1395 (3)0.0281 (8)
H360.39362.07670.10440.034*
C370.0690 (6)2.1358 (2)0.1077 (2)0.0244 (8)
H370.06692.17520.05110.029*
C380.1205 (7)2.1360 (2)0.1599 (2)0.0252 (8)
H380.25352.17570.13920.030*
C390.1148 (6)2.0778 (2)0.2431 (2)0.0214 (7)
H390.24432.07890.27860.026*
C510.6355 (6)1.4427 (2)0.4188 (2)0.0221 (7)
H51A0.78101.45420.44380.033*
H51B0.65281.38520.41310.033*
H51C0.50111.44370.45510.033*
C520.5907 (5)1.5130 (2)0.3317 (2)0.0169 (6)
H520.73121.51290.29570.020*
C530.3662 (6)1.5002 (2)0.2866 (2)0.0210 (7)
H53A0.22611.50230.32120.025*
H53B0.34531.54880.23190.025*
C540.3771 (6)1.4147 (2)0.2712 (2)0.0199 (7)
C550.1915 (6)1.3571 (2)0.2974 (2)0.0270 (8)
H550.06171.37120.32680.032*
C560.1967 (6)1.2795 (2)0.2806 (2)0.0302 (8)
H560.06931.24160.29800.036*
C570.3853 (6)1.2574 (2)0.2389 (2)0.0264 (8)
H570.38641.20530.22640.032*
C580.5734 (6)1.3121 (2)0.2154 (2)0.0234 (7)
H580.70631.29610.18860.028*
C590.5690 (6)1.3899 (2)0.2307 (2)0.0212 (7)
H590.69821.42700.21340.025*
C610.2773 (6)1.8390 (2)0.0155 (2)0.0241 (8)
H61A0.26621.78210.02250.036*
H61B0.27501.88550.07080.036*
H61C0.42571.84480.01260.036*
C620.0668 (6)1.8463 (2)0.0380 (2)0.0181 (7)
H620.08331.83380.01200.022*
C630.0560 (6)1.9360 (2)0.0462 (2)0.0202 (7)
H63A0.20221.94800.07340.024*
H63B0.08071.93540.08310.024*
C640.0316 (6)2.0087 (2)0.0382 (2)0.0187 (7)
C650.1685 (6)2.0117 (2)0.0867 (3)0.0257 (8)
H650.29271.96800.06610.031*
C660.1908 (6)2.0772 (2)0.1647 (3)0.0265 (9)
H660.33032.07800.19630.032*
C670.0122 (6)2.1413 (2)0.1967 (3)0.0222 (8)
H670.02752.18600.25000.027*
C680.1906 (6)2.1390 (2)0.1493 (3)0.0231 (8)
H680.31572.18210.17080.028*
C690.2120 (6)2.0741 (2)0.0708 (2)0.0219 (8)
H690.35042.07400.03880.026*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0149 (4)0.0286 (4)0.0238 (4)0.0002 (3)0.0020 (3)0.0123 (4)
Cl20.0184 (4)0.0175 (4)0.0292 (5)0.0041 (3)0.0007 (3)0.0042 (4)
Cl30.0159 (4)0.0193 (4)0.0221 (4)0.0018 (3)0.0022 (3)0.0074 (3)
Cl40.0146 (3)0.0194 (4)0.0205 (4)0.0010 (3)0.0025 (3)0.0038 (4)
Cl50.0218 (4)0.0171 (4)0.0239 (4)0.0034 (3)0.0064 (3)0.0067 (4)
Cl60.0176 (4)0.0209 (4)0.0259 (4)0.0021 (3)0.0013 (3)0.0065 (4)
N10.0214 (14)0.0191 (14)0.0227 (16)0.0005 (11)0.0057 (12)0.0092 (13)
N20.0184 (14)0.0227 (15)0.0293 (17)0.0036 (11)0.0017 (12)0.0104 (13)
N30.0147 (13)0.0219 (14)0.0170 (14)0.0023 (11)0.0035 (11)0.0075 (12)
N40.0147 (13)0.0175 (14)0.0252 (16)0.0031 (10)0.0018 (12)0.0083 (12)
N50.0137 (13)0.0159 (13)0.0195 (14)0.0023 (10)0.0036 (11)0.0028 (11)
N60.0137 (13)0.0166 (13)0.0226 (15)0.0022 (10)0.0021 (11)0.0053 (12)
C10.032 (2)0.028 (2)0.034 (2)0.0059 (16)0.0145 (18)0.0135 (18)
C20.0263 (18)0.0133 (15)0.0204 (18)0.0026 (13)0.0025 (14)0.0047 (14)
C30.0308 (19)0.0196 (17)0.0169 (17)0.0021 (14)0.0065 (14)0.0055 (14)
C40.0230 (18)0.0187 (17)0.0184 (18)0.0029 (14)0.0075 (15)0.0054 (14)
C50.0167 (16)0.0210 (17)0.0236 (19)0.0006 (13)0.0034 (14)0.0030 (15)
C60.0200 (17)0.0263 (19)0.0244 (19)0.0064 (14)0.0043 (14)0.0094 (16)
C70.0276 (18)0.0171 (17)0.026 (2)0.0047 (14)0.0118 (16)0.0115 (15)
C80.0225 (18)0.0213 (18)0.030 (2)0.0026 (14)0.0007 (16)0.0103 (16)
C90.0218 (17)0.0197 (17)0.0224 (19)0.0027 (14)0.0014 (15)0.0067 (15)
C110.052 (3)0.022 (2)0.042 (3)0.0041 (18)0.003 (2)0.0064 (19)
C120.0269 (19)0.035 (2)0.0187 (18)0.0052 (15)0.0022 (14)0.0008 (16)
C130.0233 (18)0.036 (2)0.028 (2)0.0033 (15)0.0006 (15)0.0084 (17)
C140.0292 (19)0.032 (2)0.0250 (19)0.0063 (15)0.0063 (15)0.0074 (16)
C150.050 (3)0.045 (3)0.039 (2)0.022 (2)0.018 (2)0.001 (2)
C160.065 (3)0.034 (2)0.045 (3)0.024 (2)0.017 (2)0.004 (2)
C170.047 (2)0.0264 (19)0.029 (2)0.0000 (16)0.0053 (17)0.0091 (16)
C180.036 (2)0.0252 (19)0.046 (2)0.0041 (15)0.0166 (18)0.0090 (18)
C190.036 (2)0.0243 (19)0.044 (2)0.0054 (16)0.0046 (18)0.0087 (18)
C210.0243 (18)0.0213 (18)0.0258 (19)0.0052 (14)0.0102 (15)0.0089 (15)
C220.0164 (15)0.0149 (15)0.0163 (16)0.0003 (12)0.0004 (13)0.0063 (13)
C230.0258 (17)0.0212 (17)0.0195 (18)0.0011 (13)0.0060 (14)0.0052 (15)
C240.0252 (17)0.0140 (15)0.0161 (16)0.0050 (12)0.0053 (14)0.0020 (13)
C250.0191 (17)0.0233 (18)0.035 (2)0.0036 (14)0.0019 (16)0.0069 (17)
C260.0180 (17)0.0275 (19)0.034 (2)0.0032 (14)0.0056 (15)0.0077 (17)
C270.0261 (18)0.0172 (17)0.024 (2)0.0054 (14)0.0044 (15)0.0044 (15)
C280.0272 (18)0.0183 (17)0.031 (2)0.0024 (14)0.0023 (16)0.0065 (16)
C290.0214 (17)0.0222 (17)0.0235 (18)0.0033 (13)0.0071 (15)0.0042 (15)
C310.0279 (19)0.029 (2)0.027 (2)0.0052 (16)0.0126 (16)0.0062 (17)
C320.0166 (15)0.0174 (16)0.0160 (16)0.0004 (12)0.0020 (14)0.0034 (14)
C330.0229 (17)0.0184 (17)0.0240 (19)0.0016 (13)0.0013 (14)0.0091 (14)
C340.0237 (17)0.0141 (16)0.0232 (19)0.0033 (13)0.0020 (15)0.0072 (15)
C350.0197 (17)0.0196 (18)0.031 (2)0.0003 (14)0.0020 (15)0.0051 (16)
C360.0265 (19)0.0261 (19)0.031 (2)0.0034 (15)0.0041 (16)0.0087 (17)
C370.0303 (19)0.0176 (17)0.024 (2)0.0077 (14)0.0029 (16)0.0051 (15)
C380.0291 (19)0.0161 (17)0.029 (2)0.0020 (14)0.0066 (16)0.0070 (15)
C390.0215 (17)0.0181 (17)0.0256 (19)0.0027 (13)0.0030 (14)0.0093 (15)
C510.0283 (18)0.0178 (16)0.0175 (17)0.0020 (13)0.0015 (14)0.0030 (14)
C520.0154 (15)0.0163 (15)0.0186 (16)0.0002 (12)0.0015 (12)0.0060 (13)
C530.0213 (16)0.0190 (16)0.0238 (18)0.0003 (12)0.0024 (13)0.0089 (14)
C540.0198 (16)0.0241 (17)0.0138 (15)0.0016 (13)0.0068 (13)0.0044 (13)
C550.0155 (16)0.030 (2)0.038 (2)0.0026 (14)0.0013 (15)0.0166 (17)
C560.0223 (18)0.0277 (19)0.043 (2)0.0042 (14)0.0064 (16)0.0151 (18)
C570.0308 (19)0.0200 (17)0.030 (2)0.0026 (14)0.0103 (16)0.0118 (15)
C580.0292 (17)0.0209 (16)0.0196 (17)0.0050 (13)0.0034 (14)0.0074 (14)
C590.0231 (16)0.0242 (17)0.0160 (16)0.0005 (13)0.0016 (13)0.0067 (14)
C610.0254 (18)0.0212 (18)0.0227 (19)0.0039 (14)0.0039 (15)0.0038 (15)
C620.0202 (16)0.0149 (16)0.0173 (17)0.0004 (12)0.0047 (14)0.0033 (13)
C630.0266 (18)0.0129 (16)0.0189 (17)0.0009 (13)0.0033 (14)0.0032 (13)
C640.0205 (16)0.0107 (15)0.0245 (19)0.0004 (12)0.0031 (15)0.0056 (14)
C650.0183 (17)0.0172 (17)0.036 (2)0.0031 (13)0.0027 (16)0.0028 (16)
C660.0209 (18)0.0183 (18)0.039 (2)0.0041 (13)0.0080 (16)0.0077 (16)
C670.0259 (19)0.0143 (17)0.024 (2)0.0054 (13)0.0019 (15)0.0033 (15)
C680.0200 (17)0.0156 (17)0.030 (2)0.0054 (13)0.0030 (15)0.0048 (15)
C690.0218 (17)0.0144 (16)0.030 (2)0.0026 (13)0.0062 (15)0.0081 (15)
Geometric parameters (Å, º) top
N1—C21.515 (4)C23—H23B0.9900
N1—H1A0.9100C24—C291.385 (5)
N1—H1B0.9100C24—C251.403 (5)
N1—H1C0.9100C25—C261.374 (5)
N2—C121.531 (5)C25—H250.9500
N2—H2A0.9100C26—C271.391 (5)
N2—H2B0.9100C26—H260.9500
N2—H2C0.9100C27—C281.385 (5)
N3—C221.494 (4)C27—H270.9500
N3—H3A0.9100C28—C291.403 (5)
N3—H3B0.9100C28—H280.9500
N3—H3C0.9100C29—H290.9500
N4—C321.497 (4)C31—C321.537 (5)
N4—H4A0.9100C31—H31A0.9800
N4—H4B0.9100C31—H31B0.9800
N4—H4C0.9100C31—H31C0.9800
N5—C521.508 (4)C32—C331.525 (4)
N5—H5A0.9100C32—H321.0000
N5—H5B0.9100C33—C341.511 (5)
N5—H5C0.9100C33—H33A0.9900
N6—C621.495 (4)C33—H33B0.9900
N6—H6A0.9100C34—C351.394 (5)
N6—H6B0.9100C34—C391.395 (5)
N6—H6C0.9100C35—C361.385 (5)
C1—C21.505 (5)C35—H350.9500
C1—H1D0.9800C36—C371.395 (5)
C1—H1E0.9800C36—H360.9500
C1—H1F0.9800C37—C381.389 (5)
C2—C31.537 (4)C37—H370.9500
C2—H21.0000C38—C391.397 (5)
C3—C41.514 (5)C38—H380.9500
C3—H3D0.9900C39—H390.9500
C3—H3E0.9900C51—C521.534 (4)
C4—C51.390 (5)C51—H51A0.9800
C4—C91.404 (5)C51—H51B0.9800
C5—C61.391 (5)C51—H51C0.9800
C5—H50.9500C52—C531.539 (4)
C6—C71.394 (5)C52—H521.0000
C6—H60.9500C53—C541.511 (5)
C7—C81.378 (6)C53—H53A0.9900
C7—H70.9500C53—H53B0.9900
C8—C91.382 (5)C54—C591.401 (5)
C8—H80.9500C54—C551.408 (5)
C9—H90.9500C55—C561.397 (5)
C11—C121.504 (5)C55—H550.9500
C11—H11A0.9800C56—C571.381 (5)
C11—H11B0.9800C56—H560.9500
C11—H11C0.9800C57—C581.388 (5)
C12—C131.521 (5)C57—H570.9500
C12—H121.0000C58—C591.388 (5)
C13—C141.543 (5)C58—H580.9500
C13—H13A0.9900C59—H590.9500
C13—H13B0.9900C61—C621.528 (5)
C14—C151.385 (5)C61—H61A0.9800
C14—C191.393 (5)C61—H61B0.9800
C15—C161.370 (6)C61—H61C0.9800
C15—H150.9500C62—C631.529 (4)
C16—C171.374 (6)C62—H621.0000
C16—H160.9500C63—C641.518 (5)
C17—C181.369 (5)C63—H63A0.9900
C17—H170.9500C63—H63B0.9900
C18—C191.380 (5)C64—C651.389 (5)
C18—H180.9500C64—C691.403 (5)
C19—H190.9500C65—C661.391 (5)
C21—C221.511 (5)C65—H650.9500
C21—H21A0.9800C66—C671.382 (5)
C21—H21B0.9800C66—H660.9500
C21—H21C0.9800C67—C681.392 (5)
C22—C231.542 (4)C67—H670.9500
C22—H221.0000C68—C691.392 (5)
C23—C241.505 (5)C68—H680.9500
C23—H23A0.9900C69—H690.9500
C2—N1—H1A109.5C29—C24—C25116.9 (3)
C2—N1—H1B109.5C29—C24—C23121.3 (3)
H1A—N1—H1B109.5C25—C24—C23121.8 (3)
C2—N1—H1C109.5C26—C25—C24122.3 (3)
H1A—N1—H1C109.5C26—C25—H25118.8
H1B—N1—H1C109.5C24—C25—H25118.8
C12—N2—H2A109.5C25—C26—C27119.9 (3)
C12—N2—H2B109.5C25—C26—H26120.0
H2A—N2—H2B109.5C27—C26—H26120.0
C12—N2—H2C109.5C28—C27—C26119.4 (4)
H2A—N2—H2C109.5C28—C27—H27120.3
H2B—N2—H2C109.5C26—C27—H27120.3
C22—N3—H3A109.5C27—C28—C29119.8 (3)
C22—N3—H3B109.5C27—C28—H28120.1
H3A—N3—H3B109.5C29—C28—H28120.1
C22—N3—H3C109.5C24—C29—C28121.7 (3)
H3A—N3—H3C109.5C24—C29—H29119.2
H3B—N3—H3C109.5C28—C29—H29119.2
C32—N4—H4A109.5C32—C31—H31A109.5
C32—N4—H4B109.5C32—C31—H31B109.5
H4A—N4—H4B109.5H31A—C31—H31B109.5
C32—N4—H4C109.5C32—C31—H31C109.5
H4A—N4—H4C109.5H31A—C31—H31C109.5
H4B—N4—H4C109.5H31B—C31—H31C109.5
C52—N5—H5A109.5N4—C32—C33110.3 (3)
C52—N5—H5B109.5N4—C32—C31107.9 (3)
H5A—N5—H5B109.5C33—C32—C31113.3 (3)
C52—N5—H5C109.5N4—C32—H32108.4
H5A—N5—H5C109.5C33—C32—H32108.4
H5B—N5—H5C109.5C31—C32—H32108.4
C62—N6—H6A109.5C34—C33—C32111.7 (3)
C62—N6—H6B109.5C34—C33—H33A109.3
H6A—N6—H6B109.5C32—C33—H33A109.3
C62—N6—H6C109.5C34—C33—H33B109.3
H6A—N6—H6C109.5C32—C33—H33B109.3
H6B—N6—H6C109.5H33A—C33—H33B107.9
C2—C1—H1D109.5C35—C34—C39117.8 (3)
C2—C1—H1E109.5C35—C34—C33120.8 (3)
H1D—C1—H1E109.5C39—C34—C33121.2 (3)
C2—C1—H1F109.5C36—C35—C34121.1 (3)
H1D—C1—H1F109.5C36—C35—H35119.4
H1E—C1—H1F109.5C34—C35—H35119.4
C1—C2—N1107.8 (3)C35—C36—C37120.6 (3)
C1—C2—C3114.1 (3)C35—C36—H36119.7
N1—C2—C3108.1 (3)C37—C36—H36119.7
C1—C2—H2108.9C38—C37—C36119.1 (4)
N1—C2—H2108.9C38—C37—H37120.4
C3—C2—H2108.9C36—C37—H37120.4
C4—C3—C2112.0 (3)C37—C38—C39119.8 (3)
C4—C3—H3D109.2C37—C38—H38120.1
C2—C3—H3D109.2C39—C38—H38120.1
C4—C3—H3E109.2C34—C39—C38121.5 (3)
C2—C3—H3E109.2C34—C39—H39119.3
H3D—C3—H3E107.9C38—C39—H39119.3
C5—C4—C9118.6 (3)C52—C51—H51A109.5
C5—C4—C3121.1 (3)C52—C51—H51B109.5
C9—C4—C3120.2 (3)H51A—C51—H51B109.5
C4—C5—C6120.5 (3)C52—C51—H51C109.5
C4—C5—H5119.7H51A—C51—H51C109.5
C6—C5—H5119.7H51B—C51—H51C109.5
C5—C6—C7120.4 (3)N5—C52—C51107.9 (3)
C5—C6—H6119.8N5—C52—C53108.6 (2)
C7—C6—H6119.8C51—C52—C53113.5 (3)
C8—C7—C6119.2 (4)N5—C52—H52108.9
C8—C7—H7120.4C51—C52—H52108.9
C6—C7—H7120.4C53—C52—H52108.9
C7—C8—C9120.9 (3)C54—C53—C52112.6 (3)
C7—C8—H8119.6C54—C53—H53A109.1
C9—C8—H8119.6C52—C53—H53A109.1
C8—C9—C4120.5 (3)C54—C53—H53B109.1
C8—C9—H9119.8C52—C53—H53B109.1
C4—C9—H9119.8H53A—C53—H53B107.8
C12—C11—H11A109.5C59—C54—C55117.7 (3)
C12—C11—H11B109.5C59—C54—C53121.9 (3)
H11A—C11—H11B109.5C55—C54—C53120.4 (3)
C12—C11—H11C109.5C56—C55—C54120.6 (3)
H11A—C11—H11C109.5C56—C55—H55119.7
H11B—C11—H11C109.5C54—C55—H55119.7
C11—C12—C13113.4 (3)C57—C56—C55120.6 (3)
C11—C12—N2109.1 (3)C57—C56—H56119.7
C13—C12—N2110.1 (3)C55—C56—H56119.7
C11—C12—H12108.0C56—C57—C58119.4 (3)
C13—C12—H12108.0C56—C57—H57120.3
N2—C12—H12108.0C58—C57—H57120.3
C12—C13—C14110.6 (3)C59—C58—C57120.6 (3)
C12—C13—H13A109.5C59—C58—H58119.7
C14—C13—H13A109.5C57—C58—H58119.7
C12—C13—H13B109.5C58—C59—C54121.1 (3)
C14—C13—H13B109.5C58—C59—H59119.5
H13A—C13—H13B108.1C54—C59—H59119.5
C15—C14—C19118.5 (4)C62—C61—H61A109.5
C15—C14—C13121.3 (4)C62—C61—H61B109.5
C19—C14—C13120.2 (3)H61A—C61—H61B109.5
C16—C15—C14120.3 (4)C62—C61—H61C109.5
C16—C15—H15119.9H61A—C61—H61C109.5
C14—C15—H15119.9H61B—C61—H61C109.5
C15—C16—C17121.0 (4)N6—C62—C61108.3 (3)
C15—C16—H16119.5N6—C62—C63108.9 (3)
C17—C16—H16119.5C61—C62—C63113.5 (3)
C18—C17—C16119.5 (4)N6—C62—H62108.7
C18—C17—H17120.2C61—C62—H62108.7
C16—C17—H17120.2C63—C62—H62108.7
C17—C18—C19120.1 (4)C64—C63—C62112.7 (3)
C17—C18—H18120.0C64—C63—H63A109.1
C19—C18—H18120.0C62—C63—H63A109.1
C18—C19—C14120.6 (4)C64—C63—H63B109.1
C18—C19—H19119.7C62—C63—H63B109.1
C14—C19—H19119.7H63A—C63—H63B107.8
C22—C21—H21A109.5C65—C64—C69117.7 (3)
C22—C21—H21B109.5C65—C64—C63121.0 (3)
H21A—C21—H21B109.5C69—C64—C63121.3 (3)
C22—C21—H21C109.5C64—C65—C66121.4 (3)
H21A—C21—H21C109.5C64—C65—H65119.3
H21B—C21—H21C109.5C66—C65—H65119.3
N3—C22—C21108.4 (3)C67—C66—C65120.7 (4)
N3—C22—C23109.1 (3)C67—C66—H66119.7
C21—C22—C23113.6 (3)C65—C66—H66119.7
N3—C22—H22108.5C66—C67—C68118.7 (4)
C21—C22—H22108.5C66—C67—H67120.6
C23—C22—H22108.5C68—C67—H67120.6
C24—C23—C22112.2 (3)C69—C68—C67120.7 (3)
C24—C23—H23A109.2C69—C68—H68119.7
C22—C23—H23A109.2C67—C68—H68119.7
C24—C23—H23B109.2C68—C69—C64120.8 (3)
C22—C23—H23B109.2C68—C69—H69119.6
H23A—C23—H23B107.9C64—C69—H69119.6
C1—C2—C3—C457.2 (4)N4—C32—C33—C34179.0 (3)
N1—C2—C3—C4177.0 (3)C31—C32—C33—C3457.9 (4)
C2—C3—C4—C569.3 (4)C32—C33—C34—C3566.7 (4)
C2—C3—C4—C9106.9 (4)C32—C33—C34—C39109.7 (4)
C9—C4—C5—C61.0 (5)C39—C34—C35—C360.1 (5)
C3—C4—C5—C6177.3 (3)C33—C34—C35—C36176.6 (3)
C4—C5—C6—C70.4 (5)C34—C35—C36—C370.8 (6)
C5—C6—C7—C80.1 (6)C35—C36—C37—C380.7 (6)
C6—C7—C8—C90.5 (6)C36—C37—C38—C390.1 (5)
C7—C8—C9—C41.2 (6)C35—C34—C39—C380.7 (5)
C5—C4—C9—C81.4 (5)C33—C34—C39—C38175.8 (3)
C3—C4—C9—C8177.7 (3)C37—C38—C39—C340.8 (5)
C11—C12—C13—C1460.7 (4)N5—C52—C53—C54179.3 (3)
N2—C12—C13—C14176.7 (3)C51—C52—C53—C5460.8 (4)
C12—C13—C14—C15115.4 (4)C52—C53—C54—C5952.7 (4)
C12—C13—C14—C1961.9 (5)C52—C53—C54—C55127.5 (3)
C19—C14—C15—C160.4 (7)C59—C54—C55—C562.2 (5)
C13—C14—C15—C16177.8 (5)C53—C54—C55—C56177.6 (3)
C14—C15—C16—C170.1 (8)C54—C55—C56—C570.8 (6)
C15—C16—C17—C181.6 (8)C55—C56—C57—C581.5 (6)
C16—C17—C18—C193.0 (7)C56—C57—C58—C592.4 (5)
C17—C18—C19—C142.8 (7)C57—C58—C59—C541.0 (5)
C15—C14—C19—C181.1 (6)C55—C54—C59—C581.3 (5)
C13—C14—C19—C18176.3 (4)C53—C54—C59—C58178.5 (3)
N3—C22—C23—C24177.6 (3)N6—C62—C63—C64178.6 (3)
C21—C22—C23—C2461.3 (4)C61—C62—C63—C6460.7 (4)
C22—C23—C24—C29113.2 (4)C62—C63—C64—C6563.9 (4)
C22—C23—C24—C2565.1 (4)C62—C63—C64—C69114.7 (4)
C29—C24—C25—C260.2 (5)C69—C64—C65—C660.3 (5)
C23—C24—C25—C26178.6 (3)C63—C64—C65—C66179.0 (3)
C24—C25—C26—C270.7 (6)C64—C65—C66—C670.6 (6)
C25—C26—C27—C280.3 (6)C65—C66—C67—C680.1 (6)
C26—C27—C28—C290.6 (5)C66—C67—C68—C690.8 (6)
C25—C24—C29—C280.7 (5)C67—C68—C69—C641.1 (6)
C23—C24—C29—C28177.7 (3)C65—C64—C69—C680.5 (5)
C27—C28—C29—C241.1 (6)C63—C64—C69—C68178.1 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl5i0.912.403.304 (3)171
N1—H1B···Cl5ii0.912.273.177 (3)171
N1—H1C···Cl6i0.912.283.181 (3)169
N2—H2A···Cl6iii0.912.273.179 (3)174
N2—H2B···Cl1iv0.912.433.215 (3)145
N2—H2C···Cl6i0.912.373.233 (3)158
N3—H3A···Cl1iv0.912.283.151 (3)159
N3—H3B···Cl10.912.223.118 (3)168
N3—H3C···Cl20.912.273.171 (3)169
N4—H4A···Cl20.912.253.149 (3)168
N4—H4B···Cl30.912.263.164 (3)172
N4—H4C···Cl2v0.912.373.271 (3)171
N5—H5A···Cl30.912.273.159 (3)165
N5—H5B···Cl40.912.363.196 (3)153
N5—H5C···Cl3iv0.912.333.233 (3)170
N6—H6A···Cl40.912.223.117 (3)167
N6—H6B···Cl5v0.912.273.168 (3)169
N6—H6C···Cl4v0.912.293.158 (3)161
Symmetry codes: (i) x, y, z+1; (ii) x1, y, z+1; (iii) x+1, y, z+1; (iv) x+1, y, z; (v) x1, y, z.
(II) (2S)-1-Phenylpropan-2-aminium bromide top
Crystal data top
C9H14N+·BrF(000) = 220
Mr = 216.12Dx = 1.432 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2ybCell parameters from 5999 reflections
a = 5.2366 (4) Åθ = 3.0–27.5°
b = 8.4264 (5) ŵ = 4.04 mm1
c = 11.3895 (8) ÅT = 100 K
β = 94.079 (2)°Blade, colourless
V = 501.30 (6) Å30.25 × 0.18 × 0.12 mm
Z = 2
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
2383 independent reflections
Radiation source: fine-focus sealed tube2343 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
Detector resolution: 28.5714 pixels mm-1θmax = 30.1°, θmin = 3.0°
profile data from ω scansh = 77
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2012)
k = 1110
Tmin = 0.711, Tmax = 1.000l = 1615
5432 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.020 w = 1/[σ2(Fo2) + (0.0329P)2 + 0.1173P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.052(Δ/σ)max = 0.001
S = 1.08Δρmax = 0.29 e Å3
2383 reflectionsΔρmin = 0.39 e Å3
115 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.045 (3)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with 962 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.003 (10)
Crystal data top
C9H14N+·BrV = 501.30 (6) Å3
Mr = 216.12Z = 2
Monoclinic, P21Mo Kα radiation
a = 5.2366 (4) ŵ = 4.04 mm1
b = 8.4264 (5) ÅT = 100 K
c = 11.3895 (8) Å0.25 × 0.18 × 0.12 mm
β = 94.079 (2)°
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
2383 independent reflections
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2012)
2343 reflections with I > 2σ(I)
Tmin = 0.711, Tmax = 1.000Rint = 0.019
5432 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.020H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.052Δρmax = 0.29 e Å3
S = 1.08Δρmin = 0.39 e Å3
2383 reflectionsAbsolute structure: Flack (1983), with 962 Friedel pairs
115 parametersAbsolute structure parameter: 0.003 (10)
1 restraint
Special details top

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 (Å2) top
xyzUiso*/Ueq
Br10.08467 (3)0.71309 (4)0.418045 (13)0.02270 (7)
N10.6129 (4)0.5569 (2)0.55110 (15)0.0206 (3)
C10.6190 (5)0.7824 (3)0.6887 (2)0.0267 (5)
H1A0.73150.84100.63890.040*
H1B0.65410.81480.77090.040*
H1C0.44000.80550.66360.040*
C20.6679 (4)0.6056 (3)0.67731 (19)0.0198 (4)
H20.85330.58540.69940.024*
C30.5097 (3)0.5028 (2)0.75640 (17)0.0202 (4)
H3A0.33260.54420.75460.024*
H3B0.50240.39270.72600.024*
C40.6258 (3)0.5028 (2)0.88157 (17)0.0187 (3)
C50.8463 (4)0.4144 (2)0.91057 (17)0.0209 (4)
H50.92080.35390.85140.025*
C60.9585 (4)0.4134 (3)1.02495 (18)0.0237 (4)
H61.10850.35241.04350.028*
C70.8511 (4)0.5017 (3)1.11225 (19)0.0262 (4)
H70.92810.50191.19030.031*
C80.6311 (4)0.5894 (3)1.08438 (19)0.0269 (4)
H80.55670.64921.14390.032*
C90.5187 (4)0.5905 (3)0.97025 (18)0.0240 (4)
H90.36800.65110.95220.029*
H1N0.649 (5)0.461 (4)0.542 (2)0.030 (7)*
H2N0.724 (5)0.604 (4)0.501 (3)0.033 (7)*
H3N0.442 (6)0.576 (4)0.524 (3)0.038 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.02399 (10)0.02052 (10)0.02300 (10)0.00361 (9)0.00246 (6)0.00244 (9)
N10.0249 (8)0.0182 (8)0.0183 (7)0.0019 (6)0.0017 (6)0.0003 (6)
C10.0379 (14)0.0202 (11)0.0209 (10)0.0013 (9)0.0059 (9)0.0007 (8)
C20.0210 (9)0.0203 (10)0.0174 (9)0.0024 (8)0.0029 (7)0.0023 (8)
C30.0175 (8)0.0216 (9)0.0210 (8)0.0022 (7)0.0029 (6)0.0018 (7)
C40.0185 (8)0.0185 (9)0.0191 (8)0.0040 (7)0.0015 (6)0.0013 (7)
C50.0217 (9)0.0221 (9)0.0190 (8)0.0006 (7)0.0018 (7)0.0017 (7)
C60.0218 (9)0.0271 (10)0.0218 (9)0.0007 (7)0.0021 (7)0.0038 (7)
C70.0318 (10)0.0258 (10)0.0204 (8)0.0069 (8)0.0030 (8)0.0029 (8)
C80.0374 (11)0.0222 (10)0.0217 (9)0.0001 (8)0.0055 (8)0.0024 (8)
C90.0257 (9)0.0206 (9)0.0258 (10)0.0035 (7)0.0029 (8)0.0015 (8)
Geometric parameters (Å, º) top
N1—C21.503 (3)C3—H3B0.9900
N1—H1N0.83 (3)C4—C51.394 (3)
N1—H2N0.93 (3)C4—C91.400 (3)
N1—H3N0.94 (3)C5—C61.391 (3)
C1—C21.519 (3)C5—H50.9500
C1—H1A0.9800C6—C71.392 (3)
C1—H1B0.9800C6—H60.9500
C1—H1C0.9800C7—C81.386 (3)
C2—C31.534 (3)C7—H70.9500
C2—H21.0000C8—C91.388 (3)
C3—C41.509 (3)C8—H80.9500
C3—H3A0.9900C9—H90.9500
C2—N1—H1N110.3 (19)C4—C3—H3B109.5
C2—N1—H2N112.5 (18)C2—C3—H3B109.5
H1N—N1—H2N100 (2)H3A—C3—H3B108.1
C2—N1—H3N112.6 (19)C5—C4—C9118.60 (18)
H1N—N1—H3N110 (3)C5—C4—C3119.65 (18)
H2N—N1—H3N111 (3)C9—C4—C3121.76 (18)
C2—C1—H1A109.5C6—C5—C4120.84 (18)
C2—C1—H1B109.5C6—C5—H5119.6
H1A—C1—H1B109.5C4—C5—H5119.6
C2—C1—H1C109.5C5—C6—C7120.05 (19)
H1A—C1—H1C109.5C5—C6—H6120.0
H1B—C1—H1C109.5C7—C6—H6120.0
N1—C2—C1109.1 (2)C8—C7—C6119.52 (19)
N1—C2—C3109.44 (17)C8—C7—H7120.2
C1—C2—C3113.74 (19)C6—C7—H7120.2
N1—C2—H2108.1C7—C8—C9120.5 (2)
C1—C2—H2108.1C7—C8—H8119.7
C3—C2—H2108.1C9—C8—H8119.7
C4—C3—C2110.88 (16)C8—C9—C4120.46 (19)
C4—C3—H3A109.5C8—C9—H9119.8
C2—C3—H3A109.5C4—C9—H9119.8
N1—C2—C3—C4158.84 (17)C4—C5—C6—C70.1 (3)
C1—C2—C3—C478.9 (2)C5—C6—C7—C80.5 (3)
C2—C3—C4—C575.2 (2)C6—C7—C8—C90.4 (3)
C2—C3—C4—C9104.5 (2)C7—C8—C9—C40.1 (3)
C9—C4—C5—C60.3 (3)C5—C4—C9—C80.3 (3)
C3—C4—C5—C6179.42 (19)C3—C4—C9—C8179.38 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Br1i0.83 (3)2.54 (3)3.3080 (19)154 (2)
N1—H2N···Br1ii0.93 (3)2.36 (3)3.2656 (19)165 (3)
N1—H3N···Br10.94 (3)2.44 (3)3.3296 (18)157 (3)
Symmetry codes: (i) x+1, y1/2, z+1; (ii) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC9H14N+·ClC9H14N+·Br
Mr171.66216.12
Crystal system, space groupTriclinic, P1Monoclinic, P21
Temperature (K)100100
a, b, c (Å)5.6396 (4), 16.3917 (11), 16.9602 (12)5.2366 (4), 8.4264 (5), 11.3895 (8)
α, β, γ (°)69.427 (4), 89.995 (5), 87.286 (5)90, 94.079 (2), 90
V3)1465.98 (18)501.30 (6)
Z62
Radiation typeMo KαMo Kα
µ (mm1)0.334.04
Crystal size (mm)0.18 × 0.06 × 0.010.25 × 0.18 × 0.12
Data collection
DiffractometerRigaku Saturn724+ (2x2 bin mode)
diffractometer
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
Absorption correctionMulti-scan
(CrystalClear-SM Expert; Rigaku, 2012)
Multi-scan
(CrystalClear-SM Expert; Rigaku, 2012)
Tmin, Tmax0.593, 1.0000.711, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
19328, 19328, 17180 5432, 2383, 2343
Rint0.00000.019
(sin θ/λ)max1)0.6990.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.129, 1.03 0.020, 0.052, 1.08
No. of reflections193282383
No. of parameters608115
No. of restraints31
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.60, 0.310.29, 0.39
Absolute structureFlack (1983), with 7328 Friedel pairsFlack (1983), with 962 Friedel pairs
Absolute structure parameter0.01 (4)0.003 (10)

Computer programs: CrystalClear-SM Expert (Rigaku, 2012), SIR92 (Altomare et al., 1994, SIR97 (Altomare et al., 1994, SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008).

Selected torsion angles (º) for (I) top
N1—C2—C3—C4177.0 (3)N4—C32—C33—C34179.0 (3)
C2—C3—C4—C569.3 (4)C31—C32—C33—C3457.9 (4)
C2—C3—C4—C9106.9 (4)C32—C33—C34—C39109.7 (4)
N2—C12—C13—C14176.7 (3)N5—C52—C53—C54179.3 (3)
C12—C13—C14—C15115.4 (4)C52—C53—C54—C5952.7 (4)
C12—C13—C14—C1961.9 (5)C52—C53—C54—C55127.5 (3)
N3—C22—C23—C24177.6 (3)N6—C62—C63—C64178.6 (3)
C21—C22—C23—C2461.3 (4)C62—C63—C64—C6563.9 (4)
C22—C23—C24—C29113.2 (4)C62—C63—C64—C69114.7 (4)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl5i0.912.403.304 (3)171.2
N1—H1B···Cl5ii0.912.273.177 (3)171.3
N1—H1C···Cl6i0.912.283.181 (3)168.7
N2—H2A···Cl6iii0.912.273.179 (3)174.4
N2—H2B···Cl1iv0.912.433.215 (3)145.0
N2—H2C···Cl6i0.912.373.233 (3)158.0
N3—H3A···Cl1iv0.912.283.151 (3)158.9
N3—H3B···Cl10.912.223.118 (3)167.9
N3—H3C···Cl20.912.273.171 (3)169.2
N4—H4A···Cl20.912.253.149 (3)167.9
N4—H4B···Cl30.912.263.164 (3)172.3
N4—H4C···Cl2v0.912.373.271 (3)170.6
N5—H5A···Cl30.912.273.159 (3)165.2
N5—H5B···Cl40.912.363.196 (3)153.4
N5—H5C···Cl3iv0.912.333.233 (3)169.8
N6—H6A···Cl40.912.223.117 (3)166.8
N6—H6B···Cl5v0.912.273.168 (3)169.4
N6—H6C···Cl4v0.912.293.158 (3)160.7
Symmetry codes: (i) x, y, z+1; (ii) x1, y, z+1; (iii) x+1, y, z+1; (iv) x+1, y, z; (v) x1, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Br1i0.83 (3)2.54 (3)3.3080 (19)154 (2)
N1—H2N···Br1ii0.93 (3)2.36 (3)3.2656 (19)165 (3)
N1—H3N···Br10.94 (3)2.44 (3)3.3296 (18)157 (3)
Symmetry codes: (i) x+1, y1/2, z+1; (ii) x+1, y, z.
 

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