Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615015867/fm3034sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015867/fm3034Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615015867/fm3034IIsup3.hkl |
CCDC references: 1420443; 1420442
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.
(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.
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).
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.
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).
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) Å3 |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.055 | H-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 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) |
C9H14N+·Cl− | γ = 87.286 (5)° |
Mr = 171.66 | V = 1465.98 (18) Å3 |
Triclinic, P1 | Z = 6 |
a = 5.6396 (4) Å | Mo Kα radiation |
b = 16.3917 (11) Å | µ = 0.33 mm−1 |
c = 16.9602 (12) Å | T = 100 K |
α = 69.427 (4)° | 0.18 × 0.06 × 0.01 mm |
β = 89.995 (5)° |
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 = 1.000 | Rint = 0.0000 |
19328 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.129 | Δρmax = 0.60 e Å−3 |
S = 1.03 | Δρmin = −0.31 e Å−3 |
19328 reflections | Absolute structure: Flack (1983), with 7328 Friedel pairs |
608 parameters | Absolute structure parameter: 0.01 (4) |
3 restraints |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cl1 | −0.06769 (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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl5i | 0.91 | 2.40 | 3.304 (3) | 171 |
N1—H1B···Cl5ii | 0.91 | 2.27 | 3.177 (3) | 171 |
N1—H1C···Cl6i | 0.91 | 2.28 | 3.181 (3) | 169 |
N2—H2A···Cl6iii | 0.91 | 2.27 | 3.179 (3) | 174 |
N2—H2B···Cl1iv | 0.91 | 2.43 | 3.215 (3) | 145 |
N2—H2C···Cl6i | 0.91 | 2.37 | 3.233 (3) | 158 |
N3—H3A···Cl1iv | 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···Cl2v | 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···Cl3iv | 0.91 | 2.33 | 3.233 (3) | 170 |
N6—H6A···Cl4 | 0.91 | 2.22 | 3.117 (3) | 167 |
N6—H6B···Cl5v | 0.91 | 2.27 | 3.168 (3) | 169 |
N6—H6C···Cl4v | 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. |
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) Å3 | 0.25 × 0.18 × 0.12 mm |
Z = 2 |
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 on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H 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 = 1.08 | Δρmax = 0.29 e Å−3 |
2383 reflections | Δρmin = −0.39 e Å−3 |
115 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/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) |
C9H14N+·Br− | V = 501.30 (6) Å3 |
Mr = 216.12 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.2366 (4) Å | µ = 4.04 mm−1 |
b = 8.4264 (5) Å | T = 100 K |
c = 11.3895 (8) Å | 0.25 × 0.18 × 0.12 mm |
β = 94.079 (2)° |
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 = 1.000 | Rint = 0.019 |
5432 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.052 | Δρmax = 0.29 e Å−3 |
S = 1.08 | Δρmin = −0.39 e Å−3 |
2383 reflections | Absolute structure: Flack (1983), with 962 Friedel pairs |
115 parameters | Absolute structure parameter: 0.003 (10) |
1 restraint |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.08467 (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)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Br1i | 0.83 (3) | 2.54 (3) | 3.3080 (19) | 154 (2) |
N1—H2N···Br1ii | 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. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C9H14N+·Cl− | C9H14N+·Br− |
Mr | 171.66 | 216.12 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21 |
Temperature (K) | 100 | 100 |
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 |
V (Å3) | 1465.98 (18) | 501.30 (6) |
Z | 6 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.33 | 4.04 |
Crystal size (mm) | 0.18 × 0.06 × 0.01 | 0.25 × 0.18 × 0.12 |
Data collection | ||
Diffractometer | Rigaku Saturn724+ (2x2 bin mode) diffractometer | Rigaku Saturn724+ (2x2 bin mode) diffractometer |
Absorption correction | Multi-scan (CrystalClear-SM Expert; Rigaku, 2012) | Multi-scan (CrystalClear-SM Expert; Rigaku, 2012) |
Tmin, Tmax | 0.593, 1.000 | 0.711, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19328, 19328, 17180 | 5432, 2383, 2343 |
Rint | 0.0000 | 0.019 |
(sin θ/λ)max (Å−1) | 0.699 | 0.705 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.129, 1.03 | 0.020, 0.052, 1.08 |
No. of reflections | 19328 | 2383 |
No. of parameters | 608 | 115 |
No. of restraints | 3 | 1 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.60, −0.31 | 0.29, −0.39 |
Absolute structure | Flack (1983), with 7328 Friedel pairs | Flack (1983), with 962 Friedel pairs |
Absolute structure parameter | 0.01 (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).
N1—C2—C3—C4 | −177.0 (3) | N4—C32—C33—C34 | −179.0 (3) |
C2—C3—C4—C5 | −69.3 (4) | C31—C32—C33—C34 | −57.9 (4) |
C2—C3—C4—C9 | 106.9 (4) | C32—C33—C34—C39 | 109.7 (4) |
N2—C12—C13—C14 | 176.7 (3) | N5—C52—C53—C54 | 179.3 (3) |
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) |
N3—C22—C23—C24 | 177.6 (3) | N6—C62—C63—C64 | 178.6 (3) |
C21—C22—C23—C24 | −61.3 (4) | C62—C63—C64—C65 | −63.9 (4) |
C22—C23—C24—C29 | 113.2 (4) | C62—C63—C64—C69 | 114.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl5i | 0.91 | 2.40 | 3.304 (3) | 171.2 |
N1—H1B···Cl5ii | 0.91 | 2.27 | 3.177 (3) | 171.3 |
N1—H1C···Cl6i | 0.91 | 2.28 | 3.181 (3) | 168.7 |
N2—H2A···Cl6iii | 0.91 | 2.27 | 3.179 (3) | 174.4 |
N2—H2B···Cl1iv | 0.91 | 2.43 | 3.215 (3) | 145.0 |
N2—H2C···Cl6i | 0.91 | 2.37 | 3.233 (3) | 158.0 |
N3—H3A···Cl1iv | 0.91 | 2.28 | 3.151 (3) | 158.9 |
N3—H3B···Cl1 | 0.91 | 2.22 | 3.118 (3) | 167.9 |
N3—H3C···Cl2 | 0.91 | 2.27 | 3.171 (3) | 169.2 |
N4—H4A···Cl2 | 0.91 | 2.25 | 3.149 (3) | 167.9 |
N4—H4B···Cl3 | 0.91 | 2.26 | 3.164 (3) | 172.3 |
N4—H4C···Cl2v | 0.91 | 2.37 | 3.271 (3) | 170.6 |
N5—H5A···Cl3 | 0.91 | 2.27 | 3.159 (3) | 165.2 |
N5—H5B···Cl4 | 0.91 | 2.36 | 3.196 (3) | 153.4 |
N5—H5C···Cl3iv | 0.91 | 2.33 | 3.233 (3) | 169.8 |
N6—H6A···Cl4 | 0.91 | 2.22 | 3.117 (3) | 166.8 |
N6—H6B···Cl5v | 0.91 | 2.27 | 3.168 (3) | 169.4 |
N6—H6C···Cl4v | 0.91 | 2.29 | 3.158 (3) | 160.7 |
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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Br1i | 0.83 (3) | 2.54 (3) | 3.3080 (19) | 154 (2) |
N1—H2N···Br1ii | 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. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register