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A second polymorph of the hydrochloride salt of the recreational drug ethylone, C
12H
16NO
3+·Cl
-, is reported [systematic name: (±)-2-ethylammonio-1-(3,4-methylenedioxyphenyl)propane-1-one chloride]. This polymorph, denoted form (
A), appears in crystallizations performed above 308 K. The originally reported form (
B) [Wood
et al. (2015).
Acta Cryst. C
71, 32-38] crystallizes preferentially at room temperature. The conformations of the cations in the two forms differ by a 180° rotation about the C-C bond linking the side chain to the aromatic ring. Hydrogen bonding links the cations and anions in both forms into similar extended chains in which any one chain contains only a single enantiomer of the chiral cation, but the packing of the ions is different. In form (
A), the aromatic rings of adjacent chains interleave, but pack equally well if neighbouring chains contain the same or opposite enantiomorph of the cation. The consequence of this is then near perfect inversion twinning in the structure. In form (
B), neighbouring chains are always inverted, leading to a centrosymmetric space group. The question as to why the polymorphs crystallize at slightly different temperatures has been examined by density functional theory (DFT) and lattice energy calculations and a consideration of packing compactness. The free energy (
G) of the crystal lattice for polymorph (
A) lies some 52 kJ mol
-1 above that of polymorph (
B).
Supporting information
CCDC reference: 1051738
Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEPII (Johnson, 1976), Mercury (Macrae et al., 2008)
and
CrystalStructure (Rigaku, 2007); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2015).
[1-(1,3-Benzodioxol-5-yl)-1-oxopropan-2-yl]ethanaminium chloride
top
Crystal data top
C12H16NO3+·Cl− | Dx = 1.366 Mg m−3 |
Mr = 257.71 | Cu Kα radiation, λ = 1.54184 Å |
Orthorhombic, P212121 | Cell parameters from 3179 reflections |
a = 6.90225 (16) Å | θ = 6.4–73.0° |
b = 7.13000 (16) Å | µ = 2.69 mm−1 |
c = 25.4692 (5) Å | T = 160 K |
V = 1253.42 (5) Å3 | Needle, pale yellow |
Z = 4 | 0.30 × 0.06 × 0.03 mm |
F(000) = 544 | |
Data collection top
Oxford Diffraction SuperNova (dual radiation) diffractometer | 2421 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 2286 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.032 |
Detector resolution: 10.3801 pixels mm-1 | θmax = 74.8°, θmin = 3.5° |
ω scans | h = −8→8 |
Absorption correction: gaussian (CrysAlisPro; Agilent, 2014) | k = −8→8 |
Tmin = 0.707, Tmax = 0.923 | l = −31→31 |
7202 measured reflections | |
Refinement top
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.067 | w = 1/[σ2(Fo2) + (0.1079P)2 + 1.0836P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.180 | (Δ/σ)max = 0.001 |
S = 1.11 | Δρmax = 0.74 e Å−3 |
2421 reflections | Δρmin = −0.34 e Å−3 |
157 parameters | Absolute structure: Refined as an inversion twin using 929 Friedel pairs |
0 restraints | Absolute structure parameter: 0.50 (5) |
Special details top
Experimental. Solvent used: 50:50 v.v. MeOH-H2O Cooling Device: Oxford Instruments Cryojet XL
Crystal mount: on a glass fibre Frames collected: 2184 Seconds exposure per
frame: 5.0–75.0 Degrees rotation per frame: 0.5 Crystal-detector distance
(mm): 55.0 Client: Stan Cameron Sample code: ethlone hydrochloride (L1407) |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refined as a 2-component inversion twin using 929 Friedel pairs |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | −0.0103 (2) | 0.35002 (17) | 0.80071 (4) | 0.0414 (4) | |
O1 | 0.1371 (7) | 0.1702 (6) | 0.58409 (15) | 0.0469 (10) | |
O2 | 0.0680 (8) | 0.4897 (6) | 0.40324 (15) | 0.0494 (11) | |
O3 | 0.0217 (6) | 0.8065 (5) | 0.41849 (13) | 0.0424 (9) | |
N1 | 0.1330 (7) | 0.2704 (6) | 0.68548 (16) | 0.0335 (9) | |
H1 | 0.0832 | 0.2945 | 0.7179 | 0.040* | |
H2 | 0.1048 | 0.1491 | 0.6774 | 0.040* | |
C1 | 0.0643 (8) | 0.4676 (8) | 0.54772 (19) | 0.0337 (11) | |
C2 | 0.0773 (9) | 0.3968 (8) | 0.4959 (2) | 0.0393 (12) | |
H21 | 0.0992 | 0.2676 | 0.4889 | 0.047* | |
C3 | 0.0565 (8) | 0.5253 (8) | 0.45632 (19) | 0.0360 (12) | |
C4 | 0.0302 (7) | 0.7116 (7) | 0.46539 (19) | 0.0333 (11) | |
C5 | 0.0214 (7) | 0.7849 (7) | 0.51485 (18) | 0.0319 (10) | |
H5 | 0.0059 | 0.9156 | 0.5206 | 0.038* | |
C6 | 0.0361 (7) | 0.6590 (7) | 0.55644 (18) | 0.0323 (10) | |
H6 | 0.0268 | 0.7042 | 0.5914 | 0.039* | |
C7 | 0.0879 (8) | 0.3315 (8) | 0.59123 (19) | 0.0343 (10) | |
C8 | 0.0363 (8) | 0.3947 (7) | 0.64665 (17) | 0.0311 (11) | |
H8 | 0.0811 | 0.5267 | 0.6520 | 0.037* | |
C9 | −0.1808 (9) | 0.3853 (9) | 0.6540 (2) | 0.0436 (14) | |
H91 | −0.2247 | 0.2557 | 0.6493 | 0.065* | |
H92 | −0.2442 | 0.4660 | 0.6280 | 0.065* | |
H93 | −0.2141 | 0.4281 | 0.6894 | 0.065* | |
C10 | 0.3466 (8) | 0.2923 (8) | 0.6877 (2) | 0.0389 (12) | |
H101 | 0.3792 | 0.4244 | 0.6957 | 0.047* | |
H102 | 0.4031 | 0.2608 | 0.6530 | 0.047* | |
C11 | 0.4327 (9) | 0.1655 (9) | 0.7293 (2) | 0.0441 (13) | |
H111 | 0.3945 | 0.0355 | 0.7224 | 0.066* | |
H112 | 0.3850 | 0.2036 | 0.7640 | 0.066* | |
H113 | 0.5742 | 0.1755 | 0.7285 | 0.066* | |
C12 | 0.0225 (9) | 0.6636 (8) | 0.37870 (19) | 0.0437 (12) | |
H121 | −0.1062 | 0.6562 | 0.3617 | 0.052* | |
H122 | 0.1203 | 0.6934 | 0.3515 | 0.052* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0673 (8) | 0.0288 (6) | 0.0282 (5) | 0.0097 (6) | 0.0067 (6) | 0.0024 (4) |
O1 | 0.075 (3) | 0.033 (2) | 0.0327 (18) | 0.004 (2) | 0.0023 (18) | −0.0044 (16) |
O2 | 0.080 (3) | 0.043 (2) | 0.0249 (17) | −0.005 (2) | 0.0033 (18) | −0.0025 (16) |
O3 | 0.059 (2) | 0.042 (2) | 0.0267 (16) | −0.006 (2) | 0.0019 (16) | 0.0035 (14) |
N1 | 0.046 (2) | 0.027 (2) | 0.0273 (18) | 0.0010 (18) | 0.0011 (17) | −0.0015 (16) |
C1 | 0.037 (2) | 0.036 (3) | 0.028 (2) | −0.005 (2) | 0.0015 (19) | −0.001 (2) |
C2 | 0.051 (3) | 0.037 (3) | 0.030 (2) | −0.006 (2) | 0.003 (2) | −0.003 (2) |
C3 | 0.040 (3) | 0.042 (3) | 0.026 (2) | −0.006 (2) | 0.0033 (19) | −0.002 (2) |
C4 | 0.033 (2) | 0.037 (3) | 0.030 (2) | −0.008 (2) | 0.0016 (18) | 0.0057 (19) |
C5 | 0.033 (2) | 0.029 (2) | 0.034 (2) | −0.002 (2) | 0.003 (2) | 0.0005 (18) |
C6 | 0.035 (2) | 0.034 (2) | 0.028 (2) | −0.004 (2) | 0.0006 (17) | −0.0041 (19) |
C7 | 0.043 (2) | 0.032 (3) | 0.028 (2) | −0.005 (2) | −0.0032 (19) | −0.001 (2) |
C8 | 0.046 (3) | 0.021 (2) | 0.026 (2) | −0.003 (2) | −0.0004 (19) | −0.0007 (16) |
C9 | 0.048 (3) | 0.050 (4) | 0.033 (3) | 0.000 (3) | 0.004 (2) | −0.001 (2) |
C10 | 0.043 (3) | 0.040 (3) | 0.033 (2) | −0.005 (2) | 0.001 (2) | 0.002 (2) |
C11 | 0.050 (3) | 0.044 (3) | 0.038 (3) | −0.005 (3) | −0.004 (2) | 0.009 (2) |
C12 | 0.059 (3) | 0.044 (3) | 0.027 (2) | −0.005 (3) | 0.000 (2) | 0.000 (2) |
Geometric parameters (Å, º) top
O1—C7 | 1.213 (7) | C5—H5 | 0.9500 |
O2—C3 | 1.378 (6) | C6—H6 | 0.9500 |
O2—C12 | 1.424 (7) | C7—C8 | 1.524 (7) |
O3—C4 | 1.374 (6) | C8—C9 | 1.511 (8) |
O3—C12 | 1.437 (6) | C8—H8 | 1.0000 |
N1—C10 | 1.484 (7) | C9—H91 | 0.9800 |
N1—C8 | 1.486 (6) | C9—H92 | 0.9800 |
N1—H1 | 0.9100 | C9—H93 | 0.9800 |
N1—H2 | 0.9100 | C10—C11 | 1.515 (8) |
C1—C6 | 1.396 (7) | C10—H101 | 0.9900 |
C1—C2 | 1.417 (7) | C10—H102 | 0.9900 |
C1—C7 | 1.482 (7) | C11—H111 | 0.9800 |
C2—C3 | 1.369 (8) | C11—H112 | 0.9800 |
C2—H21 | 0.9500 | C11—H113 | 0.9800 |
C3—C4 | 1.360 (8) | C12—H121 | 0.9900 |
C4—C5 | 1.365 (7) | C12—H122 | 0.9900 |
C5—C6 | 1.392 (7) | | |
| | | |
C3—O2—C12 | 104.9 (4) | N1—C8—C7 | 109.6 (4) |
C4—O3—C12 | 105.3 (4) | C9—C8—C7 | 109.5 (4) |
C10—N1—C8 | 114.1 (4) | N1—C8—H8 | 109.4 |
C10—N1—H1 | 108.7 | C9—C8—H8 | 109.4 |
C8—N1—H1 | 108.7 | C7—C8—H8 | 109.4 |
C10—N1—H2 | 108.7 | C8—C9—H91 | 109.5 |
C8—N1—H2 | 108.7 | C8—C9—H92 | 109.5 |
H1—N1—H2 | 107.6 | H91—C9—H92 | 109.5 |
C6—C1—C2 | 120.4 (5) | C8—C9—H93 | 109.5 |
C6—C1—C7 | 122.5 (4) | H91—C9—H93 | 109.5 |
C2—C1—C7 | 117.2 (5) | H92—C9—H93 | 109.5 |
C3—C2—C1 | 116.1 (5) | N1—C10—C11 | 110.7 (4) |
C3—C2—H21 | 121.9 | N1—C10—H101 | 109.5 |
C1—C2—H21 | 121.9 | C11—C10—H101 | 109.5 |
C4—C3—C2 | 122.9 (5) | N1—C10—H102 | 109.5 |
C4—C3—O2 | 110.7 (5) | C11—C10—H102 | 109.5 |
C2—C3—O2 | 126.3 (5) | H101—C10—H102 | 108.1 |
C3—C4—C5 | 122.4 (5) | C10—C11—H111 | 109.5 |
C3—C4—O3 | 109.8 (4) | C10—C11—H112 | 109.5 |
C5—C4—O3 | 127.7 (5) | H111—C11—H112 | 109.5 |
C4—C5—C6 | 116.9 (5) | C10—C11—H113 | 109.5 |
C4—C5—H5 | 121.6 | H111—C11—H113 | 109.5 |
C6—C5—H5 | 121.6 | H112—C11—H113 | 109.5 |
C5—C6—C1 | 121.3 (4) | O2—C12—O3 | 108.0 (4) |
C5—C6—H6 | 119.4 | O2—C12—H121 | 110.1 |
C1—C6—H6 | 119.4 | O3—C12—H121 | 110.1 |
O1—C7—C1 | 122.7 (5) | O2—C12—H122 | 110.1 |
O1—C7—C8 | 119.0 (5) | O3—C12—H122 | 110.1 |
C1—C7—C8 | 118.2 (5) | H121—C12—H122 | 108.4 |
N1—C8—C9 | 109.7 (4) | | |
| | | |
C6—C1—C2—C3 | −1.3 (8) | C2—C1—C6—C5 | −0.4 (8) |
C7—C1—C2—C3 | −179.5 (5) | C7—C1—C6—C5 | 177.6 (5) |
C1—C2—C3—C4 | 1.8 (8) | C6—C1—C7—O1 | −170.2 (5) |
C1—C2—C3—O2 | 178.5 (5) | C2—C1—C7—O1 | 7.9 (8) |
C12—O2—C3—C4 | −7.2 (6) | C6—C1—C7—C8 | 13.5 (7) |
C12—O2—C3—C2 | 175.8 (6) | C2—C1—C7—C8 | −168.3 (5) |
C2—C3—C4—C5 | −0.4 (9) | C10—N1—C8—C9 | −170.5 (4) |
O2—C3—C4—C5 | −177.5 (5) | C10—N1—C8—C7 | 69.3 (5) |
C2—C3—C4—O3 | 177.6 (5) | O1—C7—C8—N1 | 23.9 (7) |
O2—C3—C4—O3 | 0.5 (7) | C1—C7—C8—N1 | −159.8 (4) |
C12—O3—C4—C3 | 6.4 (6) | O1—C7—C8—C9 | −96.4 (6) |
C12—O3—C4—C5 | −175.8 (5) | C1—C7—C8—C9 | 79.9 (6) |
C3—C4—C5—C6 | −1.4 (8) | C8—N1—C10—C11 | 178.2 (4) |
O3—C4—C5—C6 | −179.1 (5) | C3—O2—C12—O3 | 10.9 (6) |
C4—C5—C6—C1 | 1.8 (7) | C4—O3—C12—O2 | −10.7 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1 | 0.91 | 2.24 | 3.149 (4) | 174 |
N1—H2···Cl1i | 0.91 | 2.30 | 3.134 (5) | 153 |
Symmetry code: (i) −x, y−1/2, −z+3/2. |
Relative free energies for polymorphs (A) and (B), as well as the
rotational transition state TS(AB) in the gas phase (298 K, 1 atm) and
applying SCRF-PCM for methanol and water (298 K, 1 atm)a topComputation | ΔG (kJ mol-1) |
A, gas phase | 0 |
AB, gas phase | 34 |
B, gas phase | 35 |
| |
A, MeOH | 0 |
AB, MeOH | 31 |
B, MeOH | 14 |
| |
A, HOH | 0 |
AB, HOH | 30 |
B, HOH | 12 |
(a) Computations done at 288 K and 318 K yielded essentially
the same relative energies. |
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