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α-Pyrrolidinovalero­phenone (α-PVP), a dangerous designer drug, is now being marketed around the world as a harmless `bath salt', when in reality it is a powerful β-ketone phenethyl­amine stimulant. A sample of the free base from a recent law-enforcement seizure was crystallized as the HCl salt [systematic name: 1-(1-oxo-1-phenyl­pentan-2-yl)pyrrolidin-1-ium chloride 0.786-hydrate], C15H22NO+·Cl·0.786H2O. In the crystal structure, the propyl chain is nearly perpendicular to both the phenyl ring and the carbonyl group. The hydrogen-bonding scheme involves the quaternary N atom, the Cl anion and the partially occupied (0.786) water mol­ecule, forming centrosymmetric dimers.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615023621/lg3180sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229615023621/lg3180Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615023621/lg3180Isup3.cml
Supplementary material

CCDC reference: 1411976

Introduction top

α-Pyrrolidinopentio­phenone, also known as α-pyrrolidinovalero­phenone (α-PVP), is one of several new drugs referred to on the illicit drug market as a `bath salt'; these are also called legal highs, and are entering the drug market at an accelerating pace. Analysis of these `designer drugs' and the determination of their composition are necessary in order to aid law enforcement and also to understand what potential users may be subjected to. The term `bath salts' refers to the recently emerged family of abused drugs containing one or more synthetic compounds related to cathinone, a β-ketone phenethyl­amine with stimulant properties found naturally in the khat plant (Catha edulis). α-PVP, also known on the street as flakka or gravel, is similar in structure to cathinone, but has a pyrrole ring in place of the amine group of the cathinone and a propyl group on the α-C atom. α-PVP can be synthesized from benzo­nitrile following the Heffe synthesis (Heffe, 1964; Meltzer et al., 2006).

Very little pharmacological information is available beyond anecdotal reports on recreational drug-use websites and hospital case studies (Marinetti & Antonides, 2013). Meltzer et al. (2006) investigated the use of substituted pyrovalerone analogs, including α-PVP, for the treatment of cocaine abuse by conducting dopamine-, serotonin- and norepinephrine-binding studies. This group found α-PVP to be 10–12 times more potent than cocaine in the inhibition of both dopamine and norepinephrine transport and re-uptake. However, because of the low ratio of inhibition of dopamine transport to re-uptake inhibition, α-PVP was found to be a poor cocaine antagonist. Kaizaki et al. (2014) studied the stimulatory effect of α-PVP on mice and found that the central nervous system (CNS) stimulation was comparable to methamphetamine. In humans, flakka can cause excitation and delirium, as well as hyper-stimulation, paranoia and hallucinations. It can damage the kidneys and lead to failure of these organs. Violent aggression, self-injury, suicidal tendencies and heart attacks are also not uncommon. In this work, α-PVP has been crystallized as the chloride salt 0.786-hydrate, the title compound, (I), the crystal structure of which is presented here.

Experimental top

Synthesis and crystallization top

The free base of α-PVP was obtained from law-enforcement seizures resulting from investigations of illicit bath salts. The identity was confirmed by gas chromatography/mass spectrometry (GC–MS) and compared with published data (Leffler et al. 2014; Casale & Hayes 2012). The amorphous white powder was dissolved in 10% HCl and acetone was added [What proportion of acetone is needed?]. Single crystals of (I) suitable for X-ray analysis were obtained from slow room-temperature evaporation of this solvent mixture.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were found in electron-density difference maps. The amine and water H atoms were allowed to refine, but with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N). The methyl H atoms were placed in idealized positions (tetra­hedral angles), with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C). The methyl­ene and methine H atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms, with C—H = 0.99 and 1.00 Å, respectively, and with Uiso(H) = 1.2Ueq(C). The phenyl H atoms were placed in ideal positions with C—H = 0.95 Å, and with Uiso(H) = 1.2Ueq(C). There is a positive residual electron density of 1.34 e Å-3 located 0.86 Å from the chloride anion; this is partially counterbalanced by electron density of 0.29 eÅ3- located 0.76 Å on the other side of Cl1.

Results and discussion top

α-Pyrrolidinovalero­phenone (α-PVP) belongs to a category of drugs often referred to as amphetamine-type stimulants, sharing the phenethyl­amine parent motif. This drug compound is modified by the addition of a propyl alkane at the α-C atom and a ketone at the β-C atom, and the substitution of a pyrrole in place of the amine group. These modifications are meant to enhance the psychotropic effect of the drug and to circumvent laws banning the parent compound and similar analogs. In the crystal structure of α-PVP hydro­chloride 0.786-hydrate, (I), the propyl chain extends away from the phenyl ring [dihedral angle = 82.93 (14)°], and the carbonyl unit (atoms C1/O1/C2/C8) exhibits a nearly perpendicular conformation [dihedral angle = 87.78 (12)°] (Fig. 1).

The structure of this drug shows its Cl1 counter-ion making a hydrogen bond with the quaternary N1 atom (Fig. 2). This same Cl1 anion is also hydrogen-bonded to the water molecule in the structure through two different hydrogen bonds. Fig. 2 depicts a dimer of molecules of the α-PVP cation, which forms a centrosymmetric pair across the opposite corners of a parallelogram, centered at the origin of the cell and with vertices made up of two Cl- anions and two water molecules: H2A···Cl1···H2B(-x, -y, -z) = 76.6 (14)° and H2A—O2—H2B = 102 (4)°. Fig. 3 shows a packing diagram, viewed down the b axis; the aromatic rings and, to a lesser extent, the propyl alkane chains are clustered at approximately half the a axis and propagate along the c axis. There are no ππ inter­actions between these aromatic rings.

A comparison of this structure with those of a number of other bath salts contained within the Cambridge Structural Database (CSD, Version 5.35; Groom & Allen, 2014) shows that, even though the bond between the phenyl group and the ketone group has free rotation, the conformation is essentially consistent between all cathinones. The structures of the bath salts MDPV [3,4-methyl­ene­dioxy­pyrovalerone, (RS)-1-(1,3-benzodioxol-5-yl)-2-(pyrrolidin-1-yl)pentan-1-one; Wood et al., 2015], ethyl­one [(RS)-1-(1,3-benzodioxol-5-yl)-2-(ethyl­amino)­propan-1-one; Wood et al., 2015], metaphedrone = mephedrone = 4-MMC [(RS)-2-methyl­amino-1-(4-methyl­phenyl)­propan-1-one; CSD refcodes TILLEH (Trzybiński et al., 2013) and IXOYUQ (Nycz et al., 2011)], pentedrone [(±)-1-phenyl-2-(methyl­amino)­pentan-1-one; CSD refcode TILLAD; Trzybiński et al., 2013], methyl­one [(±)-2-methyl­amino-1-(3,4-methyl­ene­dioxy­phenyl)­propan-1-one; CSD refcode IXOYOK; Nycz et al., 2011], 3,4-DMMC [(±)-1-(3,4-di­methyl­phenyl)-2-methyl­amino)­propan-1-one; CSD refcode IXOZAX; Nycz et al., 2011] and 4-MEC [(RS)-2-ethyl­amino-1-(4-methyl­phenyl)­propan-1-one; CSD refcode IXOZEB; Nycz et al., 2011] all have the ketone group out of plane with respect to the aromatic ring, on the same side of the ring in each structure, and away from the alkane chain.

As can be seen in Fig. 1, the carbonyl plane of the α-PVP component of (I) is bent at an angle of 23.10 (12)° away from the plane of the phenyl group. Except for methyl­one, where this dihedral angle is relatively small at 4.57°, all of the other structures have this dihedral angle ranging from 7.92 to 23.58°, with most of them around 20°. The significance of this similarity is that these compounds would be more likely to all have similar receptor-binding activity and therefore similar immunoassay cross-reactivity and potential physiological effects.

In conclusion, the structural elucidation of α-PVP will improve the understanding of the pharmacological properties of the compound and will assist forensic investigators in the analysis of toxicological samples and seized drug material. The information reported here contributes to the authors' continued examination of emerging drugs of abuse (Wood et al., 2015). Knowing the three-dimensional structure of novel drug compounds is key to understanding receptor binding, and to correlating structure–activity relationships, drug metabolism and the analytical profile. It will also help in the analysis of a drug's NMR spectrum and will provide a basis for rapid analyses of powder diffraction data.

Structure description top

α-Pyrrolidinopentio­phenone, also known as α-pyrrolidinovalero­phenone (α-PVP), is one of several new drugs referred to on the illicit drug market as a `bath salt'; these are also called legal highs, and are entering the drug market at an accelerating pace. Analysis of these `designer drugs' and the determination of their composition are necessary in order to aid law enforcement and also to understand what potential users may be subjected to. The term `bath salts' refers to the recently emerged family of abused drugs containing one or more synthetic compounds related to cathinone, a β-ketone phenethyl­amine with stimulant properties found naturally in the khat plant (Catha edulis). α-PVP, also known on the street as flakka or gravel, is similar in structure to cathinone, but has a pyrrole ring in place of the amine group of the cathinone and a propyl group on the α-C atom. α-PVP can be synthesized from benzo­nitrile following the Heffe synthesis (Heffe, 1964; Meltzer et al., 2006).

Very little pharmacological information is available beyond anecdotal reports on recreational drug-use websites and hospital case studies (Marinetti & Antonides, 2013). Meltzer et al. (2006) investigated the use of substituted pyrovalerone analogs, including α-PVP, for the treatment of cocaine abuse by conducting dopamine-, serotonin- and norepinephrine-binding studies. This group found α-PVP to be 10–12 times more potent than cocaine in the inhibition of both dopamine and norepinephrine transport and re-uptake. However, because of the low ratio of inhibition of dopamine transport to re-uptake inhibition, α-PVP was found to be a poor cocaine antagonist. Kaizaki et al. (2014) studied the stimulatory effect of α-PVP on mice and found that the central nervous system (CNS) stimulation was comparable to methamphetamine. In humans, flakka can cause excitation and delirium, as well as hyper-stimulation, paranoia and hallucinations. It can damage the kidneys and lead to failure of these organs. Violent aggression, self-injury, suicidal tendencies and heart attacks are also not uncommon. In this work, α-PVP has been crystallized as the chloride salt 0.786-hydrate, the title compound, (I), the crystal structure of which is presented here.

α-Pyrrolidinovalero­phenone (α-PVP) belongs to a category of drugs often referred to as amphetamine-type stimulants, sharing the phenethyl­amine parent motif. This drug compound is modified by the addition of a propyl alkane at the α-C atom and a ketone at the β-C atom, and the substitution of a pyrrole in place of the amine group. These modifications are meant to enhance the psychotropic effect of the drug and to circumvent laws banning the parent compound and similar analogs. In the crystal structure of α-PVP hydro­chloride 0.786-hydrate, (I), the propyl chain extends away from the phenyl ring [dihedral angle = 82.93 (14)°], and the carbonyl unit (atoms C1/O1/C2/C8) exhibits a nearly perpendicular conformation [dihedral angle = 87.78 (12)°] (Fig. 1).

The structure of this drug shows its Cl1 counter-ion making a hydrogen bond with the quaternary N1 atom (Fig. 2). This same Cl1 anion is also hydrogen-bonded to the water molecule in the structure through two different hydrogen bonds. Fig. 2 depicts a dimer of molecules of the α-PVP cation, which forms a centrosymmetric pair across the opposite corners of a parallelogram, centered at the origin of the cell and with vertices made up of two Cl- anions and two water molecules: H2A···Cl1···H2B(-x, -y, -z) = 76.6 (14)° and H2A—O2—H2B = 102 (4)°. Fig. 3 shows a packing diagram, viewed down the b axis; the aromatic rings and, to a lesser extent, the propyl alkane chains are clustered at approximately half the a axis and propagate along the c axis. There are no ππ inter­actions between these aromatic rings.

A comparison of this structure with those of a number of other bath salts contained within the Cambridge Structural Database (CSD, Version 5.35; Groom & Allen, 2014) shows that, even though the bond between the phenyl group and the ketone group has free rotation, the conformation is essentially consistent between all cathinones. The structures of the bath salts MDPV [3,4-methyl­ene­dioxy­pyrovalerone, (RS)-1-(1,3-benzodioxol-5-yl)-2-(pyrrolidin-1-yl)pentan-1-one; Wood et al., 2015], ethyl­one [(RS)-1-(1,3-benzodioxol-5-yl)-2-(ethyl­amino)­propan-1-one; Wood et al., 2015], metaphedrone = mephedrone = 4-MMC [(RS)-2-methyl­amino-1-(4-methyl­phenyl)­propan-1-one; CSD refcodes TILLEH (Trzybiński et al., 2013) and IXOYUQ (Nycz et al., 2011)], pentedrone [(±)-1-phenyl-2-(methyl­amino)­pentan-1-one; CSD refcode TILLAD; Trzybiński et al., 2013], methyl­one [(±)-2-methyl­amino-1-(3,4-methyl­ene­dioxy­phenyl)­propan-1-one; CSD refcode IXOYOK; Nycz et al., 2011], 3,4-DMMC [(±)-1-(3,4-di­methyl­phenyl)-2-methyl­amino)­propan-1-one; CSD refcode IXOZAX; Nycz et al., 2011] and 4-MEC [(RS)-2-ethyl­amino-1-(4-methyl­phenyl)­propan-1-one; CSD refcode IXOZEB; Nycz et al., 2011] all have the ketone group out of plane with respect to the aromatic ring, on the same side of the ring in each structure, and away from the alkane chain.

As can be seen in Fig. 1, the carbonyl plane of the α-PVP component of (I) is bent at an angle of 23.10 (12)° away from the plane of the phenyl group. Except for methyl­one, where this dihedral angle is relatively small at 4.57°, all of the other structures have this dihedral angle ranging from 7.92 to 23.58°, with most of them around 20°. The significance of this similarity is that these compounds would be more likely to all have similar receptor-binding activity and therefore similar immunoassay cross-reactivity and potential physiological effects.

In conclusion, the structural elucidation of α-PVP will improve the understanding of the pharmacological properties of the compound and will assist forensic investigators in the analysis of toxicological samples and seized drug material. The information reported here contributes to the authors' continued examination of emerging drugs of abuse (Wood et al., 2015). Knowing the three-dimensional structure of novel drug compounds is key to understanding receptor binding, and to correlating structure–activity relationships, drug metabolism and the analytical profile. It will also help in the analysis of a drug's NMR spectrum and will provide a basis for rapid analyses of powder diffraction data.

Synthesis and crystallization top

The free base of α-PVP was obtained from law-enforcement seizures resulting from investigations of illicit bath salts. The identity was confirmed by gas chromatography/mass spectrometry (GC–MS) and compared with published data (Leffler et al. 2014; Casale & Hayes 2012). The amorphous white powder was dissolved in 10% HCl and acetone was added [What proportion of acetone is needed?]. Single crystals of (I) suitable for X-ray analysis were obtained from slow room-temperature evaporation of this solvent mixture.

Refinement details top

Crystal data, data collection and structure refinement details are summarized in Table 1. All H atoms were found in electron-density difference maps. The amine and water H atoms were allowed to refine, but with Uiso(H) = 1.5Ueq(O) and 1.2Ueq(N). The methyl H atoms were placed in idealized positions (tetra­hedral angles), with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C). The methyl­ene and methine H atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms, with C—H = 0.99 and 1.00 Å, respectively, and with Uiso(H) = 1.2Ueq(C). The phenyl H atoms were placed in ideal positions with C—H = 0.95 Å, and with Uiso(H) = 1.2Ueq(C). There is a positive residual electron density of 1.34 e Å-3 located 0.86 Å from the chloride anion; this is partially counterbalanced by electron density of 0.29 eÅ3- located 0.76 Å on the other side of Cl1.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT 2014/4 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the asymmetric unit for α-PVP, showing the atomic numbering. The Cl1- counter-ion is shown in its relation to the nearest positively charged atom N1. Displacement ellipsoids are drawn at the 30% probablility level.
[Figure 2] Fig. 2. A view depicting the dimer of molecules formed when two α-PVP cations are hydrogen-bonded to their Cl- counter-ions, which are located at opposite vertices of a parallelogram formed by these two Cl- anions and the two hydrogen-bonded water molecules. Dashed lines indicate hydrogen bonds. [Symmetry code: (i) -x, -y, -z.]
[Figure 3] Fig. 3. A packing diagram showing a projection, down the b axis, of the chosen cell. The quaternary N atom, the Cl- counter-ion and the water molecule (all hydrogen bonded to each other; dashed lines) are clearly visible at the center of symmetry.
1-(1-Oxo-1-phenylpentan-2-yl)pyrrolidin-1-ium chloride 0.786-hydrate top
Crystal data top
C15H22NO+·Cl·0.786H2OF(000) = 607.4
Mr = 281.95Dx = 1.206 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54178 Å
a = 13.9428 (3) ÅCell parameters from 8883 reflections
b = 9.3285 (2) Åθ = 3.6–68.4°
c = 13.6865 (3) ŵ = 2.14 mm1
β = 119.273 (1)°T = 100 K
V = 1552.82 (6) Å3Paralellepiped, colourless
Z = 40.59 × 0.13 × 0.07 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2455 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.032
φ and ω scansθmax = 68.6°, θmin = 3.6°
Absorption correction: numerical
(SADABS; Bruker, 2009)
h = 1616
Tmin = 0.363, Tmax = 0.867k = 1011
14334 measured reflectionsl = 1616
2756 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: mixed
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 1/[σ2(Fo2) + (0.0389P)2 + 1.8447P]
where P = (Fo2 + 2Fc2)/3
2756 reflections(Δ/σ)max < 0.001
183 parametersΔρmax = 1.35 e Å3
2 restraintsΔρmin = 0.84 e Å3
Crystal data top
C15H22NO+·Cl·0.786H2OV = 1552.82 (6) Å3
Mr = 281.95Z = 4
Monoclinic, P21/cCu Kα radiation
a = 13.9428 (3) ŵ = 2.14 mm1
b = 9.3285 (2) ÅT = 100 K
c = 13.6865 (3) Å0.59 × 0.13 × 0.07 mm
β = 119.273 (1)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2756 independent reflections
Absorption correction: numerical
(SADABS; Bruker, 2009)
2455 reflections with I > 2σ(I)
Tmin = 0.363, Tmax = 0.867Rint = 0.032
14334 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0482 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.09Δρmax = 1.35 e Å3
2756 reflectionsΔρmin = 0.84 e Å3
183 parameters
Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cl10.13431 (5)0.13435 (7)0.16898 (4)0.03800 (19)
O10.33489 (13)0.05219 (16)0.47174 (12)0.0293 (4)
O20.10932 (18)0.1425 (3)0.00914 (19)0.0378 (8)0.786 (7)
H2A0.041 (4)0.139 (4)0.038 (4)0.057*0.786 (7)
H2B0.116 (3)0.075 (5)0.053 (4)0.057*0.786 (7)
N10.14861 (14)0.1979 (2)0.39803 (15)0.0239 (4)
H10.1652 (19)0.175 (3)0.341 (2)0.029*
C10.34224 (18)0.1502 (2)0.53401 (17)0.0232 (5)
C20.44313 (17)0.1747 (2)0.64323 (17)0.0228 (4)
C30.54176 (18)0.1163 (2)0.65872 (19)0.0260 (5)
H30.54300.06360.60000.031*
C40.63772 (19)0.1351 (2)0.7594 (2)0.0296 (5)
H40.70480.09520.76970.036*
C50.63592 (19)0.2122 (2)0.84538 (19)0.0298 (5)
H50.70180.22510.91450.036*
C60.53846 (19)0.2702 (2)0.83053 (18)0.0293 (5)
H60.53760.32230.88970.035*
C70.44182 (18)0.2529 (2)0.72969 (17)0.0263 (5)
H70.37520.29400.71950.032*
C80.24840 (17)0.2574 (2)0.49774 (17)0.0224 (4)
H80.23160.26990.56040.027*
C90.28388 (17)0.4024 (2)0.47324 (18)0.0244 (5)
H9A0.22090.46940.44600.029*
H9B0.34360.44170.54420.029*
C100.32375 (18)0.3978 (2)0.38745 (19)0.0281 (5)
H10A0.38710.33170.41400.034*
H10B0.26420.36040.31550.034*
C110.3578 (2)0.5459 (3)0.3688 (2)0.0369 (6)
H11A0.29420.61040.33920.055*
H11B0.38500.53910.31510.055*
H11C0.41610.58360.44010.055*
C120.10420 (19)0.0616 (3)0.4229 (2)0.0315 (5)
H12A0.14370.04050.50420.038*
H12B0.11250.02110.38230.038*
C130.01692 (19)0.0917 (3)0.3826 (2)0.0337 (6)
H13A0.06180.00440.35030.040*
H13B0.02770.12650.44490.040*
C140.04728 (19)0.2071 (3)0.29364 (19)0.0325 (5)
H14A0.05920.16600.22190.039*
H14B0.11390.26020.28080.039*
C150.05371 (18)0.3022 (3)0.34626 (19)0.0288 (5)
H15A0.05800.36230.28890.035*
H15B0.05290.36540.40400.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0438 (4)0.0534 (4)0.0259 (3)0.0135 (3)0.0241 (3)0.0088 (3)
O10.0374 (9)0.0259 (8)0.0277 (8)0.0010 (7)0.0183 (7)0.0039 (7)
O20.0227 (12)0.0512 (16)0.0340 (13)0.0005 (10)0.0094 (10)0.0035 (10)
N10.0269 (10)0.0266 (10)0.0233 (9)0.0031 (7)0.0163 (8)0.0009 (8)
C10.0317 (12)0.0208 (11)0.0246 (10)0.0019 (9)0.0196 (10)0.0020 (9)
C20.0295 (11)0.0183 (10)0.0243 (10)0.0013 (8)0.0159 (9)0.0031 (8)
C30.0327 (12)0.0195 (10)0.0311 (12)0.0011 (9)0.0195 (10)0.0009 (9)
C40.0289 (12)0.0234 (11)0.0385 (13)0.0010 (9)0.0180 (11)0.0058 (10)
C50.0327 (12)0.0237 (11)0.0277 (12)0.0030 (9)0.0105 (10)0.0061 (9)
C60.0393 (13)0.0251 (12)0.0231 (11)0.0004 (10)0.0151 (10)0.0023 (9)
C70.0315 (12)0.0244 (11)0.0253 (11)0.0042 (9)0.0157 (10)0.0041 (9)
C80.0254 (11)0.0251 (11)0.0207 (10)0.0028 (9)0.0142 (9)0.0033 (9)
C90.0237 (11)0.0229 (11)0.0261 (11)0.0003 (8)0.0118 (9)0.0017 (9)
C100.0293 (12)0.0288 (12)0.0289 (11)0.0049 (9)0.0164 (10)0.0007 (9)
C110.0341 (13)0.0331 (13)0.0457 (14)0.0013 (10)0.0212 (12)0.0098 (11)
C120.0370 (13)0.0303 (12)0.0314 (12)0.0092 (10)0.0199 (11)0.0001 (10)
C130.0350 (13)0.0403 (14)0.0329 (12)0.0127 (10)0.0221 (11)0.0075 (11)
C140.0279 (12)0.0433 (14)0.0294 (12)0.0048 (10)0.0162 (10)0.0049 (10)
C150.0266 (12)0.0342 (12)0.0279 (11)0.0002 (9)0.0151 (10)0.0027 (10)
Geometric parameters (Å, º) top
O1—C11.219 (3)C8—H81.0000
O2—H2A0.84 (5)C9—C101.526 (3)
O2—H2B0.85 (5)C9—H9A0.9900
N1—C81.500 (3)C9—H9B0.9900
N1—C151.511 (3)C10—C111.522 (3)
N1—C121.524 (3)C10—H10A0.9900
N1—H10.94 (3)C10—H10B0.9900
C1—C21.486 (3)C11—H11A0.9800
C1—C81.525 (3)C11—H11B0.9800
C2—C31.396 (3)C11—H11C0.9800
C2—C71.398 (3)C12—C131.524 (3)
C3—C41.384 (3)C12—H12A0.9900
C3—H30.9500C12—H12B0.9900
C4—C51.391 (3)C13—C141.522 (3)
C4—H40.9500C13—H13A0.9900
C5—C61.382 (3)C13—H13B0.9900
C5—H50.9500C14—C151.515 (3)
C6—C71.388 (3)C14—H14A0.9900
C6—H60.9500C14—H14B0.9900
C7—H70.9500C15—H15A0.9900
C8—C91.533 (3)C15—H15B0.9900
H2A—O2—H2B102 (4)C8—C9—H9B108.5
C8—N1—C15113.49 (17)H9A—C9—H9B107.5
C8—N1—C12113.76 (16)C11—C10—C9111.35 (19)
C15—N1—C12106.48 (16)C11—C10—H10A109.4
C8—N1—H1110.0 (15)C9—C10—H10A109.4
C15—N1—H1105.8 (15)C11—C10—H10B109.4
C12—N1—H1106.7 (15)C9—C10—H10B109.4
O1—C1—C2122.23 (19)H10A—C10—H10B108.0
O1—C1—C8119.93 (19)C10—C11—H11A109.5
C2—C1—C8117.76 (17)C10—C11—H11B109.5
C3—C2—C7119.7 (2)H11A—C11—H11B109.5
C3—C2—C1118.05 (18)C10—C11—H11C109.5
C7—C2—C1122.29 (19)H11A—C11—H11C109.5
C4—C3—C2120.2 (2)H11B—C11—H11C109.5
C4—C3—H3119.9N1—C12—C13105.34 (19)
C2—C3—H3119.9N1—C12—H12A110.7
C3—C4—C5119.9 (2)C13—C12—H12A110.7
C3—C4—H4120.0N1—C12—H12B110.7
C5—C4—H4120.0C13—C12—H12B110.7
C6—C5—C4120.1 (2)H12A—C12—H12B108.8
C6—C5—H5119.9C14—C13—C12104.20 (18)
C4—C5—H5119.9C14—C13—H13A110.9
C5—C6—C7120.5 (2)C12—C13—H13A110.9
C5—C6—H6119.8C14—C13—H13B110.9
C7—C6—H6119.8C12—C13—H13B110.9
C6—C7—C2119.6 (2)H13A—C13—H13B108.9
C6—C7—H7120.2C15—C14—C13101.74 (18)
C2—C7—H7120.2C15—C14—H14A111.4
N1—C8—C1108.67 (17)C13—C14—H14A111.4
N1—C8—C9112.49 (17)C15—C14—H14B111.4
C1—C8—C9109.46 (16)C13—C14—H14B111.4
N1—C8—H8108.7H14A—C14—H14B109.3
C1—C8—H8108.7N1—C15—C14104.08 (19)
C9—C8—H8108.7N1—C15—H15A110.9
C10—C9—C8114.93 (17)C14—C15—H15A110.9
C10—C9—H9A108.5N1—C15—H15B110.9
C8—C9—H9A108.5C14—C15—H15B110.9
C10—C9—H9B108.5H15A—C15—H15B109.0
O1—C1—C2—C320.9 (3)C12—N1—C8—C9174.02 (17)
C8—C1—C2—C3155.68 (18)O1—C1—C8—N114.0 (3)
O1—C1—C2—C7158.8 (2)C2—C1—C8—N1169.29 (16)
C8—C1—C2—C724.6 (3)O1—C1—C8—C9109.2 (2)
C7—C2—C3—C40.3 (3)C2—C1—C8—C967.5 (2)
C1—C2—C3—C4179.35 (19)N1—C8—C9—C1065.5 (2)
C2—C3—C4—C50.0 (3)C1—C8—C9—C1055.4 (2)
C3—C4—C5—C60.0 (3)C8—C9—C10—C11179.70 (19)
C4—C5—C6—C70.4 (3)C8—N1—C12—C13126.51 (19)
C5—C6—C7—C20.8 (3)C15—N1—C12—C130.7 (2)
C3—C2—C7—C60.7 (3)N1—C12—C13—C1424.7 (2)
C1—C2—C7—C6178.94 (19)C12—C13—C14—C1540.5 (2)
C15—N1—C8—C1173.42 (16)C8—N1—C15—C14151.95 (17)
C12—N1—C8—C164.6 (2)C12—N1—C15—C1426.0 (2)
C15—N1—C8—C952.1 (2)C13—C14—C15—N140.9 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.94 (3)2.21 (3)3.0997 (18)157 (2)
O2—H2A···Cl10.84 (5)2.22 (5)3.064 (2)176 (4)
O2—H2B···Cl1i0.85 (5)2.45 (5)3.291 (3)175 (4)
Symmetry code: (i) x, y, z.

Experimental details

Crystal data
Chemical formulaC15H22NO+·Cl·0.786H2O
Mr281.95
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)13.9428 (3), 9.3285 (2), 13.6865 (3)
β (°) 119.273 (1)
V3)1552.82 (6)
Z4
Radiation typeCu Kα
µ (mm1)2.14
Crystal size (mm)0.59 × 0.13 × 0.07
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionNumerical
(SADABS; Bruker, 2009)
Tmin, Tmax0.363, 0.867
No. of measured, independent and
observed [I > 2σ(I)] reflections
14334, 2756, 2455
Rint0.032
(sin θ/λ)max1)0.604
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.115, 1.09
No. of reflections2756
No. of parameters183
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.35, 0.84

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXT 2014/4 (Sheldrick, 2015a), SHELXL2014/7 (Sheldrick, 2015b), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl10.94 (3)2.21 (3)3.0997 (18)157 (2)
O2—H2A···Cl10.84 (5)2.22 (5)3.064 (2)176 (4)
O2—H2B···Cl1i0.85 (5)2.45 (5)3.291 (3)175 (4)
Symmetry code: (i) x, y, z.
 

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