Crystallographic investigations of select cathinones: emerging illicit street drugs known as `bath salts'

The name `bath salts', for an emerging class of synthetic cathinones, is derived from an attempt to evade prosecution and law enforcement. These are truly illicit drugs that have psychoactive CNS (central nervous system) stimulant effects and they have seen a rise in abuse as recreational drugs in the last few years since first having been seen in Japan in 2006. The ease of synthesis and modification of specific functional groups of the parent cathinone make these drugs particularly difficult to regulate. MDPV (3,4-methyl­ene­dioxy­pyrovalerone) is commonly encountered as its hydro­chloride salt (C<sub>16</sub>H<sub>21</sub>NO<sub>3</sub>·HCl), in either the hydrated or the anhydrous forms. This `bath salt' has various names in the US, e.g. `Super Coke', `Cloud Nine', and `Ivory Wave', to name just a few. We report here the structures of two forms of the HCl salt, one as a mixed bromide/chloride salt, C<sub>16</sub>H<sub>22</sub>NO<sub>3</sub><sup>+</sup>·0.343Br<sup>-</sup>·0.657Cl<sup>-</sup> [systematic name: 1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one bromide/chloride (0.343/0.657)], and the other with the H<sub>7</sub>O<sub>3</sub><sup>+</sup> cation, as well as the HCl counter-ion [systematic name: hydroxonium 1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one dichloride, H<sub>7</sub>O<sub>3</sub><sup>+</sup>·C<sub>16</sub>H<sub>22</sub>NO<sub>3</sub><sup>+</sup>·2Cl<sup>-</sup>]. This is one of a very few structures (11 to be exact) in which we have a new example of a precisely determined hydroxonium cation. During the course of researching the clandestine manufacture of MDPV, we were surprised by the fact that a common precursor of this illicit stimulant is known to be the fragrant species piperonal, which is present in the fragrances of orchids, most particularly in the case of the vanilla orchid. We found that MDPV can be made by a Grignard reaction of this heliotropin. This may also explain the unexpected appearance of the bromide counter-ion in some of the salts we encountered (C<sub>16</sub>H<sub>21</sub>NO<sub>3</sub>·HBr), one of which is presented here [systematic name: 1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one bro­mide, C<sub>16</sub>H<sub>22</sub>NO<sub>3</sub><sup>+</sup>·Br<sup>-</sup>]. Complexation of MDPV with a forensic crystallizing reagent, HAuCl<sub>4</sub>, yields the tetra­chlorido­aurate salt of this drug, (C<sub>16</sub>H<sub>22</sub>NO<sub>3</sub>)[AuCl<sub>4</sub>]. The heavy-metal complexing agent HAuCl<sub>4</sub> has been used for over a century to identify common quarternary nitro­gen-containing drugs via microscopic identification. Another street drug, called ethyl­one (3,4-methyl­ene­dioxy­ethyl­cathinone), is regularly sold and abused as its hydro­chloride salt (C<sub>12</sub>H<sub>15</sub>NO<sub>3</sub>·HCl), and its structure is herein described (systematic name: N-{1-[(benzo[d][1,3]dioxol-5-yl)carbon­yl]eth­yl}ethan­aminium chloride, C<sub>12</sub>H<sub>16</sub>NO<sub>3</sub><sup>+</sup>·Cl<sup>-</sup>). Marketed and sold as a `bath salt', `plant feeder', or `cleaning product', this drug is nothing more than a slight chemical modification of the banned drug methyl­one (3,4-methyl­ene­dioxy­methcathinone). As with previously popular synthetic cathinones, the abuse of ethyl­one has seen a recent increase due to regulatory efforts on previous generations of cathinones that are now banned.

S1. Introduction

`Bath salts', in this context, have nothing to do with personal hygiene products (Kyle et al., 2011), but refer to an emerging class of recreational drugs with psychoactive CNS (central nervous system) effects; this name is used mainly in the United States. In various other countries, these same designer drugs are called `plant food' and/or `plant feeders'. Designers of these type of illicit compounds incorporate slight modifications to the parent cathinone skeleton in attempts to circumvent existing drug regulations. These drugs have recently reappeared as illicit drug manufacturers have created synthetic analogs of the banned or controlled substance cathinone, a naturally occurring stimulant found in khat (Catha edulis) (Aarde et al., 2013). The prevalence and availability of these compounds through inter­net retailers has caused a dramatic rise in hospital emergency-room visits (Borek & Holstege, 2012), and deaths.

The X-ray structures of this new class of abused substances (i.e., methyl­one and other cathinones) are just now being elucidated (Nycz et al., 2011; Trzybinski et al., 2013), an example of collaborative efforts betweeen academic institutions and forensic laboratories, in order to combat the growing public health threat.

MDPV [3,4-methyl­ene­dioxy­pyrovalerone or RS)-1-(1,3-benzodioxol-5-yl)-2-(pyrrolidin-1-yl)pentan-1-one], is a cathinone-derived stimulant that has recently emerged on the illicit worldwide drug market. The reality is that MDPV is a psychoactive drug belonging to a group of β-ketone amphetamine-type stimulants. Developed and claimed by an English Patent in 1969 by Boehringer Ingelheim (1969) during an investigation of the medicinal properties of 1-(3,4-methyl­ene­dioxy­phenyl)-2-pyrrolidinoalkanones, MDPV never reached clinical usage. But, the underground drug market has taken notice.

The increased abuse of MDPV has not been overlooked. In 2011, the US Drug Enforcement Administration added MDPV and two other `bath salts', 4-methyl­methcathinone (mephedrone) and 3,4-methyl­ene­dioxy­methcathinone (methyl­one) (Drug Enforcement Administration, 2011) to the list of Schedule I Controlled Substances `due to their high potential for abuse, and lack of medical use' (Schedules of Controlled Substances, 1970). MDPV has been categorized as a pyrovalerone–cathinone due to its ability to block catecholamine uptake, which has been linked to higher addiction risks in humans (Simmler et al., 2013).

S2. Experimental

S2.1. Synthesis and crystallization

Samples of the illicit compounds (I), (II), and (IV) were obtained from law enforcement seizures. The identities of these materials were confirmed by routine mass spectrometric analyses as part of the usual forensic analytical protocol, and then were purified by recrystallization from aqueous solution to yield X-ray-quality crystals. Compound (V) was isolated from a similar procedure using aqueous HCl.

For (III), a sample of the seized illicit street drug 3,4-methyl­ene­dioxy­pyrovalerone, (I), was dissolved in water to make a 0.2% solution. To 1 ml of this drug solution was added 1 ml of 0.5% solution of HCl-acidified HAuCl₄. Crystals of (III) grew over approximately 2–4 weeks by slow evaporation at room temperature.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H atoms for all of the structures were found in electron-density difference maps. The methyl H atoms were all placed in ideally staggered positions, with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C). The methyl­ene, methine, aromatic, and amine H atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms, with C—H = 0.99, 1.00 and 0.95 Å, respectively; H atoms involved in hydrogen bonds were allowed to refine. All of the above had U_iso(H) = 1.2U_eq(C) or = 1.2U_eq(N). For (I), the Cl and Br positions were restrained by EADP and EXYZ, while the occupancies were allowed to refine; when the occupancy was determined, then the EADP and EXYZ were refined while the occupancies of these two ions were held constant.

S3. Results and discussion

The street drug MDPV has been found in drug seizures as an HCl–HBr (65.7:34.3%) salt, (I), and as the pure HBr salt, (II) (Wood et al., 2014a). The presence of the bromide counter-ion may be an artifact of the synthetic route (Boehringer Ingelheim, 1969). Both of these salts exist in the anhydrous form, and also the hydro­chloride has been crystallized in our laboratory as the hydroxonium chloride salt [C₁₆H₂₁NO₃.HCl].[H₇O₃⁺.Cl^-], (V) (Wood et al., 2014b); these structures are presented below.

The monomer of the HCl–HBr salt of MDPV (C₁₆H₂₁NO₃.0.343HBr.0.657HCl), (I), crystallizes in the space group Pbca with eight molecules per cell (see Fig. 1 for the numbering scheme). It is found to contain 34.3 (2)% HBr salt along with 65.7 (2)% HCl salt. Upon discovering the presence of Cl^- and Br^- together in the lattice of MDPV, we scanned the Cambridge Structural Database (CSD, Version ???; Allen, 2002) to ascertain whether there were other recorded examples of crystals containing both of these anions. For those having R factors less than 7.5%, we obtained seven hits, as follows: CASGEK (Kumar et al., 2011), FENJOY and FENJUE (Schneider, D. & Schier, 2004), HIYNOS (Okamoto et al., 1998), MIPPUX (Arunachalam et al., 2007), VIZNAT (Staab et al., 1991), and YIDJAW (Amini et al., 1993). All seven contain ammonium cations, suggesting that they are effective in trapping dihalide anions in their crystals. In fact, only FENJOY and FENJUE have the halide counter-ions in essentially the same overlapping coordinate positions. Schneider & Schier (2004) remarked that FENJOY is isotypic with the dibromide, iodide–bromide and diiodide analogues, while FENJUE is isotypic with the dichloride. Like FENJOY and FENJUE, MVDP has the Cl^- and Br^- ions in essentially the same coordinate positions, though with slightly different anisotropic parameters, but unlike these two previously mentioned structures, MDPV is a monocation, as is shown in Fig. 1.

The bond lengths and angles for (I), as well as for the other structures in this study, are all in the expected ranges. The dihedral angles of all of the rings and other features for these structures are presented in Table 2 for comparison purposes. The only hydrogen bond in (I) exists between the quarternary N1 atom and the anionic Cl1 atom [3.136 (3) Å], and this has an N1—H1···Cl1 angle of 155.6 (13)° (Table 3). All five of the drug structures presented here have their quarternary N cations in close contact through a hydrogen bond to either a Cl^-, a Br^-, or an AuCl₄^- anion (see Tables 3–7 for the values for each individual structure).

Fig. 2 shows the asymmetric unit of the hydro­bromide salt of MDPV, (II) (C₁₆H₂₁NO₃.HBr), with its numbering. This molecule crystallizes in the P2₁/c space group, with Z = 4 and Z' = 1. The only close-contact hydrogen-bond distance N1···Br1 is 3.198 (2) Å, and the N1—H1···Br1 angle is 171 (3)° (Table 4).

The aqueous reagent of acidified gold(III) chloride (HAuCl₄) has been used in the analytical scheme of forensic drug testing for over 150 years, precipitating crystals of unique color, morphology, and optical properties that aid the experienced examiner in drug determination. Recently, the use of the gold chloride microcrystal test for the identification of 3,4-methyl­ene­dioxy­pyrovalerone (MDPV) was described (Slivka et al., 2012). As with the products of many microcrystal tests, little is known about the resulting microcrystals beyond the characteristics observed under the polarized light microscope (McCrone, 1992).

The authors' continuing investigation into the application of HAuCl₄.3H₂O as a forensic crystallizing agent for quarternary N-containing cations (such as these bath salts are) has led to the crystallization of MDPV as the tetra­chloro­aurate(III) salt, (III). This reaffirms the widespread utility of gold chloride as a good microchemical test reagent in the analytical scheme of forensic drug identification (Wood et al., 2007, 2010; Wood & Lalancette, 2013). When MDPV is mixed with HAuCl₄.3H₂O, a salt is formed between the charged protonated amine group of the ligand and the gold anion. We describe the atomic coordination, bonding, and close contacts that contribute to the formation and structure of the 3,4-methyl­ene­dioxy­pyrovalerone tetra­chloro­aurate salt. The presence of MDPV in the illicit drug sample was confirmed by mass spectrometry using a Thermo Scientific Trace MS and compared to published data (Yohannan & Bozenko, 2010). This is the only one of the five drugs here described to crystallize in a Sohncke space group P2₁2₁2₁, with Z = 4.

Fig. 3 gives the numbering scheme for the gold ionic complex (III). The anion, AuCl₄^-, is relatively planar, with the r.m.s. deviation of all atoms from the best least-squares plane being 0.045 (3) Å. The only hydrogen bond in the structure is N1···Cl4 of 3.41 (1) Å, with an N1—H1···Cl4 angle of 151 (11)° (Table 5). There is disorder in the propyl group (shown in Fig. 3), and this has a ratio of 0.64:0.36 (3). The data crystal was racemically twinned with a refined ratio of 0.45:0.55 (2).

The fourth structure, ethyl­one, again is the HCl salt, (IV). It is a derivative of methyl­one in which the methyl group on the amine has been converted to an ethyl group; it is not banned per se in the United States, but is regulated `by inference' to methyl­one based upon structural similarity and pharmacological properties. Simmler et al. (2013) characterize the pharmacological effect of ethyl­one as cocaine–MDMA–mixed cathinone based on its inhibition of mono­amine uptake inhibitors similar to cocaine and seratonin releasers such as MDMA (3,4-methyl­ene­dioxy­methamphetamine). There is little additional information available regarding ethyl­one beyond anecdotal reports on drug user inter­net forums and supposition based upon the structural similarity to other substitued cathinones, such as methyl­one and butyl­one. The space group here is P2₁/c, with Z = 4, and one molecule in the asymmetric unit. Fig. 4 shows the numbering for (IV). The hydrogen bond formed between the quarternary N1 atom and the Cl1 ion is 3.103 (2) Å, with an N1—H1A···Cl1 angle of 161 (2)° (Table 6).

Salt (V) is MDPV.HCl.H₇O₃⁺.Cl^- (see Fig. 5). This ionic structure crystallizes in the space group P2₁/c, with Z = 4. Inter­estingly, though the elemental analysis requires the presence of an H₃O⁺ cation and two waters of crystallization, the hydroxonium cation present in this lattice has elemental composition H₇O₃⁺, as detailed next. According to a recent survey (Bernal & Watkins, 2014), there are three geometrical isomers of the hydroxonium cation with composition H₇O₃⁺, namely, those that can be formulated as H₂O–H₃O⁺–H₂O, with a clearly defined H₃O⁺ flanked by two hydrogen-bonded waters (see Fig. 6) (this is a classical V-shaped system), and a pair in which the charge is displaced from the middle to produce H₃O⁺–H₂O–H₂O or H₅O₂⁺–H₂O, the distinction being dependent on the hydrogen-bond lengths (Fig. 7). The inter­ested reader is referred to Bernal & Watkins (2014) for details.

The total number of reliable structures of cations with overall composition H₇O₃⁺ is 11 [CBZSUL01 (Roziere & Williams, 1978), GIDZEZ (Deacon, et al., 2007), HAZCAN (Jin et al., 2005), JOTQOY03 (Calleja et al., 2001), NITRAN01 (Andersen & Andersen, 1975), ODEBOO (Herzog et al., 2001), SALSUL (Mootz & Fayos, 1970), SINNAF (Ganin et al., 2006), SLBZAC10 (Attig & Mootz, 1976), SOJZOH (Stoyanov et al., 2008) and XUMQIF (Czado & Muller, 2002)], a significant number, but not excessively well represented, inasmuch as the total number of cations with composition H_xO_y⁺ (with x = 2n+1 and y = n) in the latest version of CSD (Allen, 2002) is 1406. Therefore, the serendipitous discovery of a precisely determined new example of H₂O–H₃O⁺–H₂O is described herein and its geometrical parameters and environment are as follows.

Fig. 8 gives a view of the extensive hydrogen-bonding scheme in (V) between the drug molecule itself and the two waters of hydration and the hydro­nium chloride (making the hydroxonium ion H₇O₃⁺). Note the extensive network of hydrogen-bonded hydro­nium cations and waters, where the chlorides provide additional anchoring points to the ammonium cationic drug. The network propagates indefinitely; only a small segment is shown in the figure.

The hydrogen-bond distance between the quarternary N1 atom and Cl1 ion is 3.234 (2) Å and the N1—H1···Cl1 angle is 157 (3)° (Table 7). Table 7 also presents the O···Cl and O···O distances and angles which make up the extensive hydrogen-bonded lattice in this complex.

Presented are five structures of a series of illicit drugs known on the street by various names, such as `bath salts', `Maddie', or `plant feeder'. They all have in common the basic moiety of a β-ketophenethyl­amine, with modification at the quarterary N atom, such as the pyrrole ring or alkanes of various configurations. This N atom in the drug is always presented as the HCl or HBr salt (probably for solubility aspects). We have also crystallized MDPV as the tetra­chloridoaurate salt and as the chloride salt having hydroxonium chloride (H₇O₃⁺.Cl^-) as part of an extensive hydrogen-bonded lattice. Hopefully, these structures shed more light on the chemistry and the forensic identification of these drugs.

Related literature

For related literature, see: Aarde et al. (2013); Allen (2002); Amini et al. (1993); Andersen & Andersen (1975); Arunachalam et al. (2007); Attig & Mootz (1976); Bernal & Watkins (2014); Boehringer (1969); Borek & Holstege (2012); Calleja et al. (2001); Czado & Muller (2002); Deacon et al. (2007); Drug (2011); Ganin et al. (2006); Herzog et al. (2001); Jin et al. (2005); Kumar et al. (2011); Kyle et al. (2011); McCrone (1992); Mootz & Fayos (1970); Nycz et al. (2011); Okamoto et al. (1998); Roziere & Williams (1978); Schneider & Schier (2004); Simmler et al. (2013); Slivka et al. (2012); Staab et al. (1991); Stoyanov et al. (2008); Trzybinski et al. (2013); Wood & Lalancette (2013); Wood et al. (2007, 2010, 2014a, 2014b); Yohannan & Bozenko (2010).

Computing details

For all compounds, data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008b); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures

	Fig. 1. A view of the asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms. The Br^- ion is not shown as it is in esssentially the same coordinate position (with slight changes) as the Cl^- ion (see text).
	Fig. 2. A view of the asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms.
	Fig. 3. A view of the asymmetric unit of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms. The disordered propyl group [0.64 (3):0.36 (3)] is shown with normal bonds (the 64% portion) and with open bonds (the 36% portion).
	Fig. 4. A view of the asymmetric unit of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms.
	Fig. 5. A view of the asymmetric unit of (V), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms.
	Fig. 6. The hydroxonium cation has the V-shape expected from an H3O^+ cation flanked by two hydrogen-bonded waters. Note that the H atoms that are not engaged in bonding necessary for the formation of the hydroxonium moiety are engaged in hydrogen bonding to chloride anions [symmetry codes: (i) x, -y+3/2, z-1/2; (ii) -x+2, y-1/2, z-1/2]. In contrast, its geometrical isomer, (H2O)–(H2O)–(H3O^+), is shown in Fig. 7.
	Fig. 7. This figure was drawn using the coordinates obtained from the species listed in the CSD (Allen, 2002) as SLBZAC10 (Attig & Mootz, 1976). It shows the ambiguity that may occur in describing the nature of crystalline H7O3^+ cations, as discussed in a recent review (Bernal & Watkins, 2014). On the right, there is a water with a long (1.763 Å) hydrogen bond to an H5O2^+ hydroxonium cation; that is one model. A second model is one in which, realising that H5O2^+ is itself somewhat asymmetric, the description needed is that of a terminal H3O^+ cation on the left with a H2O—H2O fragment attached to it. Again, as discussed in Bernal & Watkins (2014), the only cases in which the description is completely unambiguous is when the hydroxonium cation lies at a special position such as on a twofold axis, center of inversion etc.
	Fig. 8. A view of the extensive hydrogen-bonding scheme in (V) between the drug itself and the two waters of hydration and the hydronium chloride (making the hydroxonium ion H7O3^+). Note the extensive network of hydrogen-bonded hydronium cations and waters, where the chlorides provide additional anchoring points to the ammonium cationic drug. The network propagates infinitely throughout the crystal; what is shown here is only a small segment.

(I) 1-(Benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one bromide/chloride (0.343/0.657)

Crystal data

C16H22NO3^+·0.343(Br^−)·0.657(Cl^−)	Dx = 1.389 Mg m^−3
Mr = 327.06	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbca	Cell parameters from 9948 reflections
a = 7.0133 (5) Å	θ = 3.5–70.1°
b = 17.8399 (13) Å	µ = 2.73 mm^−1
c = 25.0044 (18) Å	T = 100 K
V = 3128.5 (4) Å^3	Plate, colourless
Z = 8	0.50 × 0.22 × 0.05 mm
F(000) = 1377.4

Data collection

Bruker SMART CCD APEXII area-detector diffractometer	2600 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
ϕ and ω scans	θmax = 70.2°, θmin = 3.5°
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	h = −7→8
Tmin = 0.400, Tmax = 0.896	k = −21→21
27721 measured reflections	l = −29→29
2859 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0355P)^2 + 1.1197P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.002
2859 reflections	Δρmax = 0.23 e Å^−3
204 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2014), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00029 (6)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	1.2980 (3)	0.17033 (17)	0.15215 (11)	0.0151 (9)	0.6568
Br1	1.2981 (4)	0.16938 (17)	0.15208 (12)	0.0306 (11)	0.3432
O1	0.90394 (13)	0.07940 (5)	0.05485 (4)	0.0235 (2)
O2	0.21449 (14)	−0.11780 (6)	0.08320 (4)	0.0320 (3)
O3	0.34965 (14)	−0.19493 (5)	0.01853 (4)	0.0256 (2)
N1	0.85333 (17)	0.15400 (6)	0.14626 (4)	0.0192 (2)
H1	0.979 (3)	0.1464 (8)	0.1413 (6)	0.023*
C1	0.66150 (18)	−0.01211 (7)	0.06467 (5)	0.0183 (3)
C2	0.48103 (19)	−0.02830 (7)	0.08732 (5)	0.0207 (3)
H2	0.4266	0.0023	0.1144	0.025*
C3	0.38964 (18)	−0.09027 (7)	0.06808 (5)	0.0209 (3)
C4	0.46855 (19)	−0.13593 (7)	0.02905 (5)	0.0203 (3)
C5	0.6420 (2)	−0.12096 (7)	0.00609 (5)	0.0221 (3)
H5	0.6944	−0.1521	−0.0210	0.027*
C6	0.7374 (2)	−0.05753 (7)	0.02474 (5)	0.0210 (3)
H6	0.8576	−0.0450	0.0098	0.025*
C7	0.77859 (18)	0.05254 (7)	0.08261 (5)	0.0185 (3)
C8	0.74521 (19)	0.08217 (7)	0.13902 (5)	0.0194 (3)
H8	0.6061	0.0927	0.1436	0.023*
C9	0.79433 (19)	0.21617 (7)	0.10770 (6)	0.0224 (3)
H9A	0.8996	0.2281	0.0827	0.027*
H9B	0.6813	0.2008	0.0866	0.027*
C10	0.7478 (2)	0.28363 (8)	0.14276 (6)	0.0271 (3)
H10A	0.6092	0.2865	0.1501	0.033*
H10B	0.7894	0.3308	0.1255	0.033*
C11	0.8599 (2)	0.26915 (8)	0.19427 (6)	0.0281 (3)
H11A	0.9963	0.2820	0.1899	0.034*
H11B	0.8067	0.2980	0.2246	0.034*
C12	0.8329 (2)	0.18580 (8)	0.20211 (6)	0.0244 (3)
H12A	0.7053	0.1747	0.2171	0.029*
H12B	0.9314	0.1651	0.2263	0.029*
C13	0.80501 (19)	0.02272 (8)	0.18023 (5)	0.0234 (3)
H13A	0.7866	0.0437	0.2165	0.028*
H13B	0.7193	−0.0211	0.1767	0.028*
C14	1.0107 (2)	−0.00422 (8)	0.17520 (6)	0.0291 (3)
H14A	1.0355	−0.0193	0.1377	0.035*
H14B	1.0981	0.0375	0.1841	0.035*
C15	1.0513 (2)	−0.07005 (8)	0.21202 (7)	0.0345 (4)
H15A	1.0288	−0.0550	0.2492	0.052*
H15B	1.1845	−0.0857	0.2078	0.052*
H15C	0.9670	−0.1119	0.2028	0.052*
C16	0.1791 (2)	−0.18174 (8)	0.04995 (6)	0.0248 (3)
H16A	0.0690	−0.1721	0.0261	0.030*
H16B	0.1500	−0.2261	0.0723	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0017 (12)	0.0238 (17)	0.0198 (16)	−0.0012 (9)	0.0016 (8)	0.0049 (12)
Br1	0.0275 (17)	0.0298 (18)	0.0344 (19)	0.0013 (10)	0.0026 (10)	−0.0015 (12)
O1	0.0264 (5)	0.0213 (5)	0.0227 (5)	−0.0016 (4)	0.0077 (4)	−0.0013 (4)
O2	0.0241 (6)	0.0309 (6)	0.0409 (6)	−0.0083 (4)	0.0080 (4)	−0.0151 (5)
O3	0.0249 (5)	0.0230 (5)	0.0288 (5)	−0.0019 (4)	−0.0008 (4)	−0.0075 (4)
N1	0.0189 (6)	0.0195 (6)	0.0192 (6)	−0.0012 (5)	0.0020 (4)	−0.0030 (4)
C1	0.0225 (7)	0.0171 (6)	0.0154 (6)	0.0022 (5)	−0.0006 (5)	0.0006 (5)
C2	0.0222 (7)	0.0202 (6)	0.0197 (6)	0.0025 (5)	0.0009 (5)	−0.0027 (5)
C3	0.0192 (7)	0.0218 (7)	0.0217 (7)	0.0009 (5)	−0.0005 (5)	0.0005 (5)
C4	0.0253 (7)	0.0167 (6)	0.0190 (7)	0.0025 (5)	−0.0052 (5)	−0.0005 (5)
C5	0.0277 (7)	0.0198 (7)	0.0189 (7)	0.0040 (5)	0.0015 (5)	−0.0028 (5)
C6	0.0237 (7)	0.0203 (7)	0.0190 (7)	0.0022 (5)	0.0034 (5)	0.0011 (5)
C7	0.0193 (7)	0.0169 (6)	0.0192 (7)	0.0037 (5)	0.0012 (5)	0.0015 (5)
C8	0.0193 (6)	0.0193 (7)	0.0196 (7)	−0.0026 (5)	0.0025 (5)	−0.0021 (5)
C9	0.0262 (8)	0.0185 (7)	0.0225 (7)	0.0002 (5)	0.0019 (5)	0.0002 (6)
C10	0.0295 (7)	0.0204 (7)	0.0314 (8)	0.0005 (6)	0.0035 (6)	−0.0040 (6)
C11	0.0283 (8)	0.0248 (7)	0.0312 (8)	−0.0021 (6)	0.0018 (6)	−0.0118 (6)
C12	0.0268 (8)	0.0273 (7)	0.0190 (7)	−0.0010 (6)	0.0013 (5)	−0.0069 (6)
C13	0.0306 (8)	0.0221 (7)	0.0176 (7)	−0.0046 (5)	0.0016 (5)	0.0016 (5)
C14	0.0315 (8)	0.0259 (7)	0.0299 (8)	0.0018 (6)	−0.0005 (6)	0.0061 (6)
C15	0.0420 (9)	0.0245 (7)	0.0369 (9)	−0.0055 (6)	−0.0143 (7)	0.0048 (6)
C16	0.0242 (7)	0.0222 (7)	0.0279 (8)	−0.0030 (5)	−0.0015 (6)	−0.0046 (6)

Geometric parameters (Å, º)

O1—C7	1.2183 (16)	C9—C10	1.5245 (19)
O2—C3	1.3759 (16)	C9—H9A	0.9900
O2—C16	1.4333 (17)	C9—H9B	0.9900
O3—C4	1.3683 (16)	C10—C11	1.531 (2)
O3—C16	1.4501 (17)	C10—H10A	0.9900
N1—C8	1.5000 (16)	C10—H10B	0.9900
N1—C12	1.5141 (17)	C11—C12	1.5116 (19)
N1—C9	1.5268 (17)	C11—H11A	0.9900
N1—H1	0.902 (18)	C11—H11B	0.9900
C1—C6	1.3915 (18)	C12—H12A	0.9900
C1—C2	1.4164 (19)	C12—H12B	0.9900
C1—C7	1.4851 (18)	C13—C14	1.525 (2)
C2—C3	1.3653 (18)	C13—H13A	0.9900
C2—H2	0.9500	C13—H13B	0.9900
C3—C4	1.3865 (18)	C14—C15	1.519 (2)
C4—C5	1.3716 (19)	C14—H14A	0.9900
C5—C6	1.3946 (19)	C14—H14B	0.9900
C5—H5	0.9500	C15—H15A	0.9800
C6—H6	0.9500	C15—H15B	0.9800
C7—C8	1.5245 (18)	C15—H15C	0.9800
C8—C13	1.5371 (18)	C16—H16A	0.9900
C8—H8	1.0000	C16—H16B	0.9900
C3—O2—C16	106.22 (10)	C9—C10—H10A	111.0
C4—O3—C16	105.89 (10)	C11—C10—H10A	111.0
C8—N1—C12	112.56 (10)	C9—C10—H10B	111.0
C8—N1—C9	114.04 (10)	C11—C10—H10B	111.0
C12—N1—C9	106.54 (10)	H10A—C10—H10B	109.0
C8—N1—H1	110.5 (10)	C12—C11—C10	102.16 (11)
C12—N1—H1	106.0 (10)	C12—C11—H11A	111.3
C9—N1—H1	106.7 (10)	C10—C11—H11A	111.3
C6—C1—C2	120.65 (12)	C12—C11—H11B	111.3
C6—C1—C7	117.23 (12)	C10—C11—H11B	111.3
C2—C1—C7	122.12 (11)	H11A—C11—H11B	109.2
C3—C2—C1	116.34 (12)	C11—C12—N1	103.72 (11)
C3—C2—H2	121.8	C11—C12—H12A	111.0
C1—C2—H2	121.8	N1—C12—H12A	111.0
C2—C3—O2	127.69 (12)	C11—C12—H12B	111.0
C2—C3—C4	122.43 (13)	N1—C12—H12B	111.0
O2—C3—C4	109.88 (11)	H12A—C12—H12B	109.0
O3—C4—C5	127.58 (12)	C14—C13—C8	114.84 (11)
O3—C4—C3	110.12 (12)	C14—C13—H13A	108.6
C5—C4—C3	122.29 (12)	C8—C13—H13A	108.6
C4—C5—C6	116.31 (12)	C14—C13—H13B	108.6
C4—C5—H5	121.8	C8—C13—H13B	108.6
C6—C5—H5	121.8	H13A—C13—H13B	107.5
C1—C6—C5	121.95 (13)	C15—C14—C13	111.79 (13)
C1—C6—H6	119.0	C15—C14—H14A	109.3
C5—C6—H6	119.0	C13—C14—H14A	109.3
O1—C7—C1	122.17 (12)	C15—C14—H14B	109.3
O1—C7—C8	120.10 (11)	C13—C14—H14B	109.3
C1—C7—C8	117.64 (11)	H14A—C14—H14B	107.9
N1—C8—C7	109.29 (10)	C14—C15—H15A	109.5
N1—C8—C13	111.75 (11)	C14—C15—H15B	109.5
C7—C8—C13	109.83 (10)	H15A—C15—H15B	109.5
N1—C8—H8	108.6	C14—C15—H15C	109.5
C7—C8—H8	108.6	H15A—C15—H15C	109.5
C13—C8—H8	108.6	H15B—C15—H15C	109.5
C10—C9—N1	105.56 (11)	O2—C16—O3	107.50 (10)
C10—C9—H9A	110.6	O2—C16—H16A	110.2
N1—C9—H9A	110.6	O3—C16—H16A	110.2
C10—C9—H9B	110.6	O2—C16—H16B	110.2
N1—C9—H9B	110.6	O3—C16—H16B	110.2
H9A—C9—H9B	108.8	H16A—C16—H16B	108.5
C9—C10—C11	103.92 (11)
C6—C1—C2—C3	0.48 (19)	C12—N1—C8—C7	−178.05 (11)
C7—C1—C2—C3	−178.63 (12)	C9—N1—C8—C7	60.42 (14)
C1—C2—C3—O2	−179.89 (12)	C12—N1—C8—C13	−56.28 (14)
C1—C2—C3—C4	0.85 (19)	C9—N1—C8—C13	−177.80 (10)
C16—O2—C3—C2	177.78 (13)	O1—C7—C8—N1	12.32 (17)
C16—O2—C3—C4	−2.88 (15)	C1—C7—C8—N1	−171.13 (11)
C16—O3—C4—C5	−175.48 (13)	O1—C7—C8—C13	−110.60 (13)
C16—O3—C4—C3	4.77 (14)	C1—C7—C8—C13	65.94 (14)
C2—C3—C4—O3	178.12 (12)	C8—N1—C9—C10	126.74 (12)
O2—C3—C4—O3	−1.26 (15)	C12—N1—C9—C10	1.94 (14)
C2—C3—C4—C5	−1.6 (2)	N1—C9—C10—C11	23.49 (14)
O2—C3—C4—C5	178.98 (12)	C9—C10—C11—C12	−40.10 (14)
O3—C4—C5—C6	−178.75 (12)	C10—C11—C12—N1	41.25 (14)
C3—C4—C5—C6	0.97 (19)	C8—N1—C12—C11	−152.67 (11)
C2—C1—C6—C5	−1.1 (2)	C9—N1—C12—C11	−26.97 (14)
C7—C1—C6—C5	178.03 (12)	N1—C8—C13—C14	−65.13 (15)
C4—C5—C6—C1	0.4 (2)	C7—C8—C13—C14	56.33 (15)
C6—C1—C7—O1	21.76 (19)	C8—C13—C14—C15	−172.24 (12)
C2—C1—C7—O1	−159.10 (12)	C3—O2—C16—O3	5.72 (15)
C6—C1—C7—C8	−154.71 (12)	C4—O3—C16—O2	−6.45 (14)
C2—C1—C7—C8	24.43 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.902 (18)	2.292 (18)	3.136 (3)	155.6 (13)

(II) 1-(Benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one bromide

Crystal data

C16H22NO3^+·Br^−	F(000) = 736
Mr = 356.25	Dx = 1.485 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 7.1280 (1) Å	Cell parameters from 9953 reflections
b = 21.3335 (5) Å	θ = 4.1–69.8°
c = 10.5243 (2) Å	µ = 3.60 mm^−1
β = 95.118 (1)°	T = 293 K
V = 1594.00 (5) Å^3	Needle, colourless
Z = 4	0.43 × 0.18 × 0.06 mm

Data collection

Bruker SMART CCD APEXII area-detector diffractometer	2813 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
ϕ and ω scans	θmax = 69.8°, θmin = 4.1°
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	h = −8→8
Tmin = 0.307, Tmax = 0.813	k = −24→25
14889 measured reflections	l = −12→12
2942 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: mixed
wR(F^2) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.087P)^2 + 3.9741P] where P = (Fo^2 + 2Fc^2)/3
2942 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.69 e Å^−3
1 restraint	Δρmin = −1.24 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Br1	0.24512 (4)	0.11423 (2)	0.51185 (3)	0.02080 (17)
O1	0.6359 (3)	0.16662 (10)	0.7789 (2)	0.0126 (4)
O2	1.0762 (3)	0.22853 (10)	1.1743 (2)	0.0133 (5)
O3	1.3764 (3)	0.19542 (10)	1.1351 (2)	0.0148 (5)
N1	0.6950 (4)	0.10850 (11)	0.5502 (2)	0.0078 (5)
H1	0.573 (3)	0.1110 (16)	0.549 (4)	0.009*
C1	0.9461 (4)	0.14754 (13)	0.8689 (3)	0.0084 (6)
C2	0.9151 (4)	0.18242 (13)	0.9796 (3)	0.0092 (6)
H2	0.7950	0.1954	0.9960	0.011*
C3	1.0692 (4)	0.19605 (13)	1.0611 (3)	0.0088 (6)
C4	1.2490 (4)	0.17612 (14)	1.0389 (3)	0.0101 (6)
C5	1.2829 (4)	0.14139 (14)	0.9337 (3)	0.0116 (6)
H5	1.4035	0.1278	0.9201	0.014*
C6	1.1270 (4)	0.12737 (14)	0.8474 (3)	0.0103 (6)
H6	1.1444	0.1042	0.7746	0.012*
C7	0.7821 (4)	0.13681 (13)	0.7753 (3)	0.0088 (6)
C8	0.7882 (4)	0.08502 (13)	0.6750 (3)	0.0081 (6)
H8	0.9188	0.0730	0.6654	0.010*
C9	0.7556 (4)	0.17352 (14)	0.5109 (3)	0.0120 (6)
H9A	0.8801	0.1834	0.5508	0.014*
H9B	0.6677	0.2050	0.5357	0.014*
C10	0.7572 (5)	0.17139 (15)	0.3656 (3)	0.0156 (6)
H10A	0.8850	0.1741	0.3412	0.019*
H10B	0.6844	0.2058	0.3262	0.019*
C11	0.6680 (5)	0.10822 (14)	0.3247 (3)	0.0129 (6)
H11A	0.5320	0.1115	0.3106	0.015*
H11B	0.7174	0.0926	0.2478	0.015*
C12	0.7266 (4)	0.06627 (14)	0.4390 (3)	0.0107 (6)
H12A	0.6485	0.0290	0.4390	0.013*
H12B	0.8577	0.0539	0.4400	0.013*
C13	0.6757 (4)	0.02809 (13)	0.7171 (3)	0.0109 (6)
H13A	0.5467	0.0411	0.7245	0.013*
H13B	0.6734	−0.0036	0.6509	0.013*
C14	0.7526 (4)	−0.00147 (14)	0.8432 (3)	0.0133 (6)
H14A	0.7680	0.0309	0.9080	0.016*
H14B	0.6617	−0.0315	0.8697	0.016*
C15	0.9409 (5)	−0.03448 (15)	0.8345 (3)	0.0183 (7)
H15A	0.9280	−0.0654	0.7681	0.027*
H15B	0.9788	−0.0545	0.9144	0.027*
H15C	1.0344	−0.0043	0.8157	0.027*
C16	1.2736 (4)	0.23485 (15)	1.2172 (3)	0.0152 (6)
H16A	1.2965	0.2215	1.3053	0.018*
H16B	1.3130	0.2782	1.2110	0.018*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0163 (2)	0.0259 (3)	0.0200 (2)	0.00014 (12)	0.00035 (15)	−0.00320 (13)
O1	0.0092 (10)	0.0141 (10)	0.0141 (10)	0.0013 (8)	−0.0015 (8)	−0.0017 (8)
O2	0.0131 (11)	0.0171 (11)	0.0091 (10)	0.0002 (8)	−0.0019 (8)	−0.0055 (8)
O3	0.0119 (10)	0.0201 (11)	0.0111 (10)	0.0011 (8)	−0.0054 (8)	−0.0054 (9)
N1	0.0088 (12)	0.0066 (11)	0.0075 (12)	−0.0004 (9)	−0.0015 (10)	0.0016 (9)
C1	0.0105 (13)	0.0060 (12)	0.0083 (13)	−0.0012 (10)	−0.0010 (11)	0.0022 (10)
C2	0.0100 (13)	0.0072 (12)	0.0101 (14)	0.0013 (10)	0.0002 (11)	0.0008 (11)
C3	0.0137 (14)	0.0065 (13)	0.0061 (13)	−0.0010 (10)	−0.0001 (11)	−0.0001 (10)
C4	0.0113 (14)	0.0094 (13)	0.0087 (13)	−0.0023 (10)	−0.0041 (11)	0.0025 (11)
C5	0.0101 (14)	0.0141 (14)	0.0104 (14)	−0.0001 (11)	−0.0002 (11)	0.0003 (12)
C6	0.0117 (14)	0.0108 (13)	0.0083 (14)	−0.0010 (11)	0.0006 (11)	0.0006 (11)
C7	0.0096 (14)	0.0073 (13)	0.0093 (14)	−0.0024 (10)	−0.0003 (11)	0.0019 (11)
C8	0.0095 (13)	0.0083 (13)	0.0058 (13)	−0.0007 (10)	−0.0029 (10)	0.0017 (11)
C9	0.0175 (16)	0.0053 (14)	0.0128 (15)	−0.0034 (10)	−0.0012 (12)	0.0035 (10)
C10	0.0187 (16)	0.0165 (15)	0.0112 (15)	−0.0047 (12)	−0.0014 (12)	0.0051 (12)
C11	0.0149 (15)	0.0155 (15)	0.0078 (14)	0.0004 (11)	−0.0015 (12)	0.0021 (11)
C12	0.0132 (14)	0.0100 (13)	0.0085 (14)	0.0000 (11)	−0.0020 (11)	−0.0019 (11)
C13	0.0134 (14)	0.0086 (13)	0.0101 (14)	−0.0028 (11)	−0.0020 (11)	0.0017 (11)
C14	0.0197 (15)	0.0106 (14)	0.0090 (14)	−0.0024 (11)	−0.0021 (12)	0.0033 (11)
C15	0.0224 (17)	0.0124 (14)	0.0186 (16)	0.0010 (12)	−0.0065 (13)	0.0057 (12)
C16	0.0155 (15)	0.0178 (15)	0.0113 (14)	−0.0006 (12)	−0.0042 (12)	−0.0049 (12)

Geometric parameters (Å, º)

O1—C7	1.225 (4)	C9—C10	1.531 (4)
O2—C3	1.375 (3)	C9—H9A	0.9700
O2—C16	1.445 (4)	C9—H9B	0.9700
O3—C4	1.362 (4)	C10—C11	1.535 (4)
O3—C16	1.451 (4)	C10—H10A	0.9700
N1—C8	1.504 (3)	C10—H10B	0.9700
N1—C12	1.510 (4)	C11—C12	1.527 (4)
N1—C9	1.521 (4)	C11—H11A	0.9700
N1—H1	0.868 (19)	C11—H11B	0.9700
C1—C6	1.397 (4)	C12—H12A	0.9700
C1—C2	1.417 (4)	C12—H12B	0.9700
C1—C7	1.477 (4)	C13—C14	1.526 (4)
C2—C3	1.364 (4)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C4	1.390 (4)	C14—C15	1.526 (4)
C4—C5	1.372 (4)	C14—H14A	0.9700
C5—C6	1.403 (4)	C14—H14B	0.9700
C5—H5	0.9300	C15—H15A	0.9600
C6—H6	0.9300	C15—H15B	0.9600
C7—C8	1.531 (4)	C15—H15C	0.9600
C8—C13	1.542 (4)	C16—H16A	0.9700
C8—H8	0.9800	C16—H16B	0.9700
C3—O2—C16	106.1 (2)	C9—C10—H10A	110.7
C4—O3—C16	106.2 (2)	C11—C10—H10A	110.7
C8—N1—C12	113.2 (2)	C9—C10—H10B	110.7
C8—N1—C9	115.3 (2)	C11—C10—H10B	110.7
C12—N1—C9	105.5 (2)	H10A—C10—H10B	108.8
C8—N1—H1	113 (3)	C12—C11—C10	102.5 (2)
C12—N1—H1	104 (2)	C12—C11—H11A	111.3
C9—N1—H1	104 (2)	C10—C11—H11A	111.3
C6—C1—C2	120.6 (3)	C12—C11—H11B	111.3
C6—C1—C7	122.1 (3)	C10—C11—H11B	111.3
C2—C1—C7	117.2 (3)	H11A—C11—H11B	109.2
C3—C2—C1	117.0 (3)	N1—C12—C11	102.2 (2)
C3—C2—H2	121.5	N1—C12—H12A	111.3
C1—C2—H2	121.5	C11—C12—H12A	111.3
C2—C3—O2	128.1 (3)	N1—C12—H12B	111.3
C2—C3—C4	122.2 (3)	C11—C12—H12B	111.3
O2—C3—C4	109.7 (2)	H12A—C12—H12B	109.2
O3—C4—C5	127.6 (3)	C14—C13—C8	114.8 (2)
O3—C4—C3	110.3 (3)	C14—C13—H13A	108.6
C5—C4—C3	122.2 (3)	C8—C13—H13A	108.6
C4—C5—C6	116.8 (3)	C14—C13—H13B	108.6
C4—C5—H5	121.6	C8—C13—H13B	108.6
C6—C5—H5	121.6	H13A—C13—H13B	107.5
C1—C6—C5	121.3 (3)	C15—C14—C13	112.9 (3)
C1—C6—H6	119.3	C15—C14—H14A	109.0
C5—C6—H6	119.3	C13—C14—H14A	109.0
O1—C7—C1	121.6 (3)	C15—C14—H14B	109.0
O1—C7—C8	118.2 (3)	C13—C14—H14B	109.0
C1—C7—C8	120.1 (2)	H14A—C14—H14B	107.8
N1—C8—C7	108.9 (2)	C14—C15—H15A	109.5
N1—C8—C13	108.2 (2)	C14—C15—H15B	109.5
C7—C8—C13	108.8 (2)	H15A—C15—H15B	109.5
N1—C8—H8	110.3	C14—C15—H15C	109.5
C7—C8—H8	110.3	H15A—C15—H15C	109.5
C13—C8—H8	110.3	H15B—C15—H15C	109.5
N1—C9—C10	105.8 (2)	O2—C16—O3	106.8 (2)
N1—C9—H9A	110.6	O2—C16—H16A	110.4
C10—C9—H9A	110.6	O3—C16—H16A	110.4
N1—C9—H9B	110.6	O2—C16—H16B	110.4
C10—C9—H9B	110.6	O3—C16—H16B	110.4
H9A—C9—H9B	108.7	H16A—C16—H16B	108.6
C9—C10—C11	105.4 (2)
C6—C1—C2—C3	1.3 (4)	C12—N1—C8—C7	168.7 (2)
C7—C1—C2—C3	−175.4 (2)	C9—N1—C8—C7	47.0 (3)
C1—C2—C3—O2	−179.5 (3)	C12—N1—C8—C13	−73.1 (3)
C1—C2—C3—C4	−1.0 (4)	C9—N1—C8—C13	165.2 (2)
C16—O2—C3—C2	−174.9 (3)	O1—C7—C8—N1	43.0 (3)
C16—O2—C3—C4	6.4 (3)	C1—C7—C8—N1	−140.3 (3)
C16—O3—C4—C5	175.3 (3)	O1—C7—C8—C13	−74.8 (3)
C16—O3—C4—C3	−5.4 (3)	C1—C7—C8—C13	101.9 (3)
C2—C3—C4—O3	−179.4 (3)	C8—N1—C9—C10	144.1 (2)
O2—C3—C4—O3	−0.6 (3)	C12—N1—C9—C10	18.4 (3)
C2—C3—C4—C5	−0.1 (5)	N1—C9—C10—C11	8.5 (3)
O2—C3—C4—C5	178.7 (3)	C9—C10—C11—C12	−31.6 (3)
O3—C4—C5—C6	−180.0 (3)	C8—N1—C12—C11	−165.1 (2)
C3—C4—C5—C6	0.8 (4)	C9—N1—C12—C11	−38.1 (3)
C2—C1—C6—C5	−0.6 (4)	C10—C11—C12—N1	42.8 (3)
C7—C1—C6—C5	176.0 (3)	N1—C8—C13—C14	180.0 (2)
C4—C5—C6—C1	−0.5 (4)	C7—C8—C13—C14	−61.7 (3)
C6—C1—C7—O1	−162.3 (3)	C8—C13—C14—C15	−69.0 (3)
C2—C1—C7—O1	14.4 (4)	C3—O2—C16—O3	−9.6 (3)
C6—C1—C7—C8	21.1 (4)	C4—O3—C16—O2	9.2 (3)
C2—C1—C7—C8	−162.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br1	0.87 (2)	2.34 (2)	3.198 (2)	171 (3)

(III) 1-(Benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one tetrachloridoaurate

Crystal data

(C16H22NO3)[AuCl4]	Dx = 1.990 Mg m^−3
Mr = 615.11	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P212121	Cell parameters from 9955 reflections
a = 10.5046 (4) Å	θ = 2.5–67.5°
b = 11.1534 (4) Å	µ = 18.40 mm^−1
c = 17.5193 (6) Å	T = 100 K
V = 2052.60 (13) Å^3	Rod, orange
Z = 4	0.23 × 0.19 × 0.11 mm
F(000) = 1184

Data collection

Bruker SMART CCD APEXII area-detector diffractometer	3479 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.047
ϕ and ω scans	θmax = 69.5°, θmin = 4.7°
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	h = −11→12
Tmin = 0.101, Tmax = 0.237	k = −13→13
24150 measured reflections	l = −19→20
3554 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0361P)^2 + 26.5568P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3554 reflections	Δρmax = 1.66 e Å^−3
250 parameters	Δρmin = −2.42 e Å^−3
37 restraints	Absolute structure: Refined as an inversion twin.
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.45 (3)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Au1	−0.25988 (5)	0.56871 (4)	0.73961 (3)	0.02131 (17)
Cl1	−0.1087 (3)	0.4661 (3)	0.6703 (2)	0.0243 (8)
Cl2	−0.4186 (3)	0.4495 (3)	0.68729 (18)	0.0165 (6)
Cl3	−0.4104 (3)	0.6774 (3)	0.8065 (2)	0.0208 (7)
Cl4	−0.1020 (3)	0.6797 (3)	0.7969 (2)	0.0238 (7)
O1	0.1064 (9)	0.4066 (8)	0.8349 (6)	0.028 (2)
O2	0.2999 (8)	0.0654 (9)	0.9967 (5)	0.030 (2)
O3	0.5179 (10)	0.0964 (10)	0.9978 (6)	0.039 (3)
N1	0.1920 (10)	0.5795 (9)	0.7451 (6)	0.026 (2)
H1	0.114 (5)	0.581 (13)	0.769 (6)	0.031*
C1	0.3050 (13)	0.3437 (11)	0.8823 (8)	0.021 (3)
C2	0.2480 (18)	0.2434 (10)	0.9192 (6)	0.027 (3)
H2	0.1587	0.2302	0.9191	0.032*
C3	0.3314 (14)	0.1671 (12)	0.9549 (8)	0.026 (3)
C4	0.4579 (13)	0.1849 (13)	0.9577 (8)	0.026 (3)
C5	0.5162 (14)	0.2821 (14)	0.9232 (8)	0.032 (3)
H5	0.6059	0.2928	0.9239	0.038*
C6	0.4347 (15)	0.3633 (14)	0.8872 (8)	0.031 (3)
H6	0.4695	0.4341	0.8655	0.037*
C7	0.2178 (13)	0.4277 (12)	0.8428 (7)	0.026 (3)
C8	0.2704 (16)	0.5474 (11)	0.8150 (7)	0.032 (3)
H8A	0.3603	0.5456	0.8052	0.038*	0.5133
H8AA	0.3531	0.5284	0.7950	0.038*	0.4867
C9	0.2175 (14)	0.4997 (12)	0.6775 (7)	0.028 (3)
H9A	0.1628	0.4275	0.6794	0.034*
H9B	0.3077	0.4740	0.6768	0.034*
C10	0.1869 (17)	0.5748 (19)	0.6073 (9)	0.052 (5)
H10A	0.1162	0.5386	0.5779	0.062*
H10B	0.2623	0.5819	0.5738	0.062*
C11	0.1477 (15)	0.6995 (15)	0.6394 (11)	0.044 (4)
H11A	0.1796	0.7649	0.6063	0.053*
H11B	0.0540	0.7062	0.6437	0.053*
C12	0.2085 (16)	0.7042 (13)	0.7159 (8)	0.039 (4)
H12A	0.1653	0.7630	0.7494	0.047*
H12B	0.2998	0.7255	0.7118	0.047*
C13	0.231 (4)	0.651 (2)	0.8644 (10)	0.047 (9)	0.51 (4)
H13A	0.1721	0.6997	0.8330	0.51 (4)*	0.51 (4)
H13B	0.3084	0.7003	0.8716	0.51 (4)*	0.51 (4)
C13A	0.297 (3)	0.633 (2)	0.8819 (13)	0.011 (6)	0.49 (4)
H13C	0.3906	0.6428	0.8788	0.487*	0.49 (4)
H13D	0.2617	0.7094	0.8629	0.487*	0.49 (4)
C14	0.169 (3)	0.642 (2)	0.9432 (12)	0.044 (10)	0.51 (4)
H14A	0.1837	0.5604	0.9640	0.51 (4)*	0.51 (4)
H14B	0.0759	0.6531	0.9379	0.51 (4)*	0.51 (4)
C14A	0.279 (3)	0.640 (2)	0.9466 (12)	0.042 (10)	0.49 (4)
H14C	0.3638	0.6246	0.9692	0.487*	0.49 (4)
H14D	0.2284	0.5669	0.9580	0.487*	0.49 (4)
C15	0.221 (2)	0.7347 (14)	0.9993 (10)	0.065 (6)
H15A	0.1593	0.7477	1.0403	0.097*	0.51 (4)
H15B	0.2366	0.8103	0.9724	0.097*	0.51 (4)
H15C	0.3013	0.7054	1.0212	0.097*	0.51 (4)
H15D	0.3055	0.7612	0.9823	0.097*	0.49 (4)
H15E	0.2282	0.6986	1.0501	0.097*	0.49 (4)
H15F	0.1635	0.8036	1.0014	0.097*	0.49 (4)
C16	0.4192 (15)	0.0127 (15)	1.0181 (9)	0.036 (4)
H16A	0.4318	−0.0641	0.9909	0.043*
H16B	0.4209	−0.0030	1.0737	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Au1	0.0199 (3)	0.0167 (2)	0.0274 (3)	−0.0004 (2)	0.0005 (2)	0.00284 (18)
Cl1	0.0191 (16)	0.0164 (15)	0.037 (2)	0.0031 (12)	0.0047 (13)	0.0007 (13)
Cl2	0.0132 (13)	0.0117 (13)	0.0247 (15)	−0.0056 (11)	0.0005 (11)	−0.0017 (12)
Cl3	0.0115 (14)	0.0198 (16)	0.0309 (18)	0.0015 (12)	0.0082 (13)	−0.0100 (14)
Cl4	0.0222 (17)	0.0199 (16)	0.0293 (18)	−0.0017 (13)	−0.0045 (14)	−0.0008 (14)
O1	0.027 (6)	0.025 (5)	0.031 (5)	−0.004 (4)	−0.007 (4)	0.000 (4)
O2	0.031 (5)	0.026 (5)	0.032 (5)	−0.006 (5)	−0.008 (4)	0.005 (4)
O3	0.032 (6)	0.051 (7)	0.034 (6)	−0.007 (5)	−0.007 (5)	0.017 (5)
N1	0.026 (5)	0.023 (5)	0.029 (6)	0.009 (5)	0.009 (5)	0.001 (5)
C1	0.026 (7)	0.013 (6)	0.025 (7)	−0.006 (5)	0.009 (5)	0.001 (5)
C2	0.036 (8)	0.024 (6)	0.021 (6)	0.004 (8)	0.000 (8)	−0.005 (4)
C3	0.040 (9)	0.021 (7)	0.017 (7)	0.000 (6)	0.000 (6)	0.000 (5)
C4	0.023 (7)	0.031 (8)	0.023 (7)	−0.007 (6)	0.000 (6)	−0.003 (6)
C5	0.022 (8)	0.044 (9)	0.028 (8)	−0.008 (7)	0.002 (6)	0.001 (7)
C6	0.034 (9)	0.039 (8)	0.020 (7)	−0.006 (7)	0.004 (6)	0.000 (6)
C7	0.031 (8)	0.021 (6)	0.025 (6)	−0.001 (7)	0.003 (5)	−0.005 (5)
C8	0.051 (10)	0.024 (6)	0.021 (6)	−0.006 (7)	−0.005 (7)	−0.001 (5)
C9	0.029 (9)	0.030 (7)	0.024 (7)	0.006 (6)	−0.001 (6)	−0.002 (5)
C10	0.047 (10)	0.073 (13)	0.034 (9)	−0.021 (11)	−0.003 (7)	0.016 (10)
C11	0.021 (8)	0.043 (9)	0.068 (12)	0.001 (7)	−0.004 (8)	0.029 (9)
C12	0.051 (10)	0.030 (7)	0.037 (8)	0.008 (7)	0.017 (7)	0.018 (6)
C13	0.052 (15)	0.040 (12)	0.050 (13)	0.001 (11)	0.004 (12)	−0.001 (10)
C13A	0.012 (7)	0.011 (7)	0.011 (7)	−0.001 (3)	−0.002 (3)	0.001 (3)
C14	0.038 (15)	0.038 (13)	0.055 (15)	−0.002 (10)	−0.008 (11)	−0.011 (11)
C14A	0.042 (15)	0.038 (13)	0.046 (14)	0.002 (10)	−0.016 (11)	−0.007 (10)
C15	0.091 (17)	0.042 (10)	0.060 (11)	−0.009 (11)	0.035 (12)	−0.014 (8)
C16	0.024 (8)	0.048 (9)	0.035 (9)	−0.005 (7)	−0.005 (7)	0.007 (7)

Geometric parameters (Å, º)

Au1—Cl4	2.300 (3)	C9—H9B	0.9900
Au1—Cl1	2.304 (3)	C10—C11	1.56 (3)
Au1—Cl3	2.312 (3)	C10—H10A	0.9900
Au1—Cl2	2.321 (3)	C10—H10B	0.9900
O1—C7	1.201 (16)	C11—C12	1.48 (2)
O2—C3	1.389 (16)	C11—H11A	0.9900
O2—C16	1.434 (18)	C11—H11B	0.9900
O3—C4	1.366 (17)	C12—H12A	0.9900
O3—C16	1.439 (18)	C12—H12B	0.9900
N1—C12	1.492 (17)	C13—C14	1.529 (3)
N1—C9	1.505 (16)	C13—H13A	0.9900
N1—C8	1.519 (17)	C13—H13B	0.9900
N1—H1	0.920 (3)	C13A—C14A	1.15 (3)
C1—C6	1.38 (2)	C13A—H13C	0.9900
C1—C2	1.424 (18)	C13A—H13D	0.9900
C1—C7	1.482 (19)	C14—C15	1.530 (3)
C2—C3	1.37 (2)	C14—H14A	0.9900
C2—H2	0.9500	C14—H14B	0.9900
C3—C4	1.34 (2)	C14A—C15	1.531 (3)
C4—C5	1.38 (2)	C14A—H14C	0.9900
C5—C6	1.40 (2)	C14A—H14D	0.9900
C5—H5	0.9500	C15—H15A	0.9800
C6—H6	0.9500	C15—H15B	0.9800
C7—C8	1.525 (18)	C15—H15C	0.9800
C8—C13	1.50 (2)	C15—H15D	0.9800
C8—C13A	1.54 (2)	C15—H15E	0.9800
C8—H8A	0.9601	C15—H15F	0.9800
C8—H8AA	0.9603	C16—H16A	0.9900
C9—C10	1.52 (2)	C16—H16B	0.9900
C9—H9A	0.9900
Cl4—Au1—Cl1	90.02 (12)	C10—C11—H11B	110.9
Cl4—Au1—Cl3	89.41 (10)	H11A—C11—H11B	109.0
Cl1—Au1—Cl3	178.02 (13)	C11—C12—N1	103.1 (13)
Cl4—Au1—Cl2	176.92 (12)	C11—C12—H12A	111.1
Cl1—Au1—Cl2	90.13 (10)	N1—C12—H12A	111.1
Cl3—Au1—Cl2	90.54 (11)	C11—C12—H12B	111.1
C3—O2—C16	105.3 (11)	N1—C12—H12B	111.1
C4—O3—C16	105.3 (11)	H12A—C12—H12B	109.1
C12—N1—C9	105.1 (10)	C8—C13—C14	126 (2)
C12—N1—C8	115.6 (11)	C8—C13—H13A	105.8
C9—N1—C8	113.5 (9)	C14—C13—H13A	105.8
C12—N1—H1	104 (9)	C8—C13—H13B	105.8
C9—N1—H1	122 (8)	C14—C13—H13B	105.8
C8—N1—H1	96 (7)	H13A—C13—H13B	106.2
C6—C1—C2	120.7 (14)	C14A—C13A—C8	140 (3)
C6—C1—C7	122.6 (12)	C14A—C13A—H13C	102.1
C2—C1—C7	116.6 (12)	C8—C13A—H13C	102.1
C3—C2—C1	115.2 (15)	C14A—C13A—H13D	102.1
C3—C2—H2	122.4	C8—C13A—H13D	102.1
C1—C2—H2	122.4	H13C—C13A—H13D	104.8
C4—C3—C2	123.7 (14)	C13—C14—C15	112.4 (15)
C4—C3—O2	109.7 (12)	C13—C14—H14A	109.1
C2—C3—O2	126.5 (14)	C15—C14—H14A	109.1
C3—C4—O3	111.6 (12)	C13—C14—H14B	109.1
C3—C4—C5	122.5 (14)	C15—C14—H14B	109.1
O3—C4—C5	125.9 (13)	H14A—C14—H14B	107.8
C4—C5—C6	115.7 (14)	C13A—C14A—C15	135 (2)
C4—C5—H5	122.1	C13A—C14A—H14C	103.5
C6—C5—H5	122.1	C15—C14A—H14C	103.5
C1—C6—C5	122.0 (14)	C13A—C14A—H14D	103.5
C1—C6—H6	119.0	C15—C14A—H14D	103.5
C5—C6—H6	119.0	H14C—C14A—H14D	105.3
O1—C7—C1	122.2 (12)	C14—C15—C14A	44.4 (18)
O1—C7—C8	119.2 (12)	C14—C15—H15A	109.5
C1—C7—C8	118.6 (12)	C14A—C15—H15A	143.9
C13—C8—N1	97.7 (14)	C14—C15—H15B	109.5
C13—C8—C7	112.9 (15)	C14A—C15—H15B	103.9
N1—C8—C7	105.5 (11)	H15A—C15—H15B	109.5
C13—C8—C13A	30.0 (13)	C14—C15—H15C	109.5
N1—C8—C13A	124.7 (14)	C14A—C15—H15C	70.4
C7—C8—C13A	111.4 (13)	H15A—C15—H15C	109.5
C13—C8—H8A	113.0	H15B—C15—H15C	109.5
N1—C8—H8A	113.3	C14—C15—H15D	109.5
C7—C8—H8A	113.3	C14A—C15—H15D	70.6
C13A—C8—H8A	88.3	H15A—C15—H15D	141.1
C13—C8—H8AA	129.0	H15B—C15—H15D	56.3
N1—C8—H8AA	104.4	H15C—C15—H15D	56.3
C7—C8—H8AA	104.5	C14—C15—H15E	109.5
C13A—C8—H8AA	104.5	C14A—C15—H15E	103.6
H8A—C8—H8AA	16.3	H15A—C15—H15E	56.3
N1—C9—C10	105.8 (12)	H15B—C15—H15E	141.1
N1—C9—H9A	110.6	H15C—C15—H15E	56.3
C10—C9—H9A	110.6	H15D—C15—H15E	109.5
N1—C9—H9B	110.6	C14—C15—H15F	109.5
C10—C9—H9B	110.6	C14A—C15—H15F	144.2
H9A—C9—H9B	108.7	H15A—C15—H15F	56.3
C9—C10—C11	104.9 (13)	H15B—C15—H15F	56.3
C9—C10—H10A	110.8	H15C—C15—H15F	141.1
C11—C10—H10A	110.8	H15D—C15—H15F	109.5
C9—C10—H10B	110.8	H15E—C15—H15F	109.5
C11—C10—H10B	110.8	O2—C16—O3	107.4 (12)
H10A—C10—H10B	108.9	O2—C16—H16A	110.2
C12—C11—C10	104.1 (13)	O3—C16—H16A	110.2
C12—C11—H11A	110.9	O2—C16—H16B	110.2
C10—C11—H11A	110.9	O3—C16—H16B	110.2
C12—C11—H11B	110.9	H16A—C16—H16B	108.5
C6—C1—C2—C3	−3.5 (18)	C9—N1—C8—C13A	159.7 (16)
C7—C1—C2—C3	179.7 (11)	O1—C7—C8—C13	73 (2)
C1—C2—C3—C4	1.7 (19)	C1—C7—C8—C13	−104.4 (19)
C1—C2—C3—O2	177.9 (11)	O1—C7—C8—N1	−33.0 (15)
C16—O2—C3—C4	−6.8 (15)	C1—C7—C8—N1	150.1 (11)
C16—O2—C3—C2	176.5 (13)	O1—C7—C8—C13A	104.9 (17)
C2—C3—C4—O3	179.0 (12)	C1—C7—C8—C13A	−72.0 (18)
O2—C3—C4—O3	2.3 (16)	C12—N1—C9—C10	−25.8 (14)
C2—C3—C4—C5	−1 (2)	C8—N1—C9—C10	−153.1 (12)
O2—C3—C4—C5	−177.8 (12)	N1—C9—C10—C11	1.7 (15)
C16—O3—C4—C3	3.3 (16)	C9—C10—C11—C12	23.1 (16)
C16—O3—C4—C5	−176.6 (15)	C10—C11—C12—N1	−39.0 (15)
C3—C4—C5—C6	2 (2)	C9—N1—C12—C11	40.7 (14)
O3—C4—C5—C6	−178.1 (13)	C8—N1—C12—C11	166.7 (12)
C2—C1—C6—C5	5 (2)	N1—C8—C13—C14	123 (3)
C7—C1—C6—C5	−178.5 (13)	C7—C8—C13—C14	12 (4)
C4—C5—C6—C1	−4 (2)	C13A—C8—C13—C14	−81 (3)
C6—C1—C7—O1	175.5 (13)	C13—C8—C13A—C14A	89 (4)
C2—C1—C7—O1	−7.7 (18)	N1—C8—C13A—C14A	118 (3)
C6—C1—C7—C8	−7.7 (19)	C7—C8—C13A—C14A	−10 (4)
C2—C1—C7—C8	169.1 (10)	C8—C13—C14—C15	139 (3)
C12—N1—C8—C13	52.4 (18)	C8—C13A—C14A—C15	−127 (4)
C9—N1—C8—C13	174.0 (16)	C13—C14—C15—C14A	−52.5 (17)
C12—N1—C8—C7	168.8 (11)	C13A—C14A—C15—C14	77 (4)
C9—N1—C8—C7	−69.6 (14)	C3—O2—C16—O3	8.7 (15)
C12—N1—C8—C13A	38 (2)	C4—O3—C16—O2	−7.4 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl4	0.92 (1)	2.57 (7)	3.41 (1)	151 (11)

(IV) N-{1-[(Benzo[d][1,3]dioxol-5-yl)carbonyl]ethyl}ethanaminium chloride

Crystal data

C12H16NO3^+·Cl^−	F(000) = 544
Mr = 257.71	Dx = 1.334 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 10.6159 (4) Å	Cell parameters from 9152 reflections
b = 7.1060 (3) Å	θ = 4.3–70.1°
c = 17.6348 (6) Å	µ = 2.62 mm^−1
β = 105.3310 (18)°	T = 100 K
V = 1282.97 (9) Å^3	Block, colourless
Z = 4	0.33 × 0.31 × 0.15 mm

Data collection

Bruker SMART CCD APEXII area-detector diffractometer	2097 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
ϕ and ω scans	θmax = 70.1°, θmin = 4.3°
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	h = −12→12
Tmin = 0.475, Tmax = 0.696	k = −8→8
9602 measured reflections	l = −21→21
2253 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: mixed
wR(F^2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.20	w = 1/[σ^2(Fo^2) + (0.0393P)^2 + 1.4462P] where P = (Fo^2 + 2Fc^2)/3
2253 reflections	(Δ/σ)max < 0.001
162 parameters	Δρmax = 0.36 e Å^−3
2 restraints	Δρmin = −0.26 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.15694 (5)	1.27762 (7)	0.29089 (3)	0.01916 (17)
O1	0.36322 (15)	0.8936 (2)	0.40504 (9)	0.0229 (4)
O2	0.29141 (16)	0.1995 (2)	0.58561 (9)	0.0261 (4)
O3	0.45735 (15)	0.3175 (2)	0.68818 (9)	0.0243 (4)
N1	0.13611 (18)	0.8424 (3)	0.29510 (10)	0.0165 (4)
H1A	0.157 (2)	0.964 (3)	0.3047 (14)	0.020*
H1B	0.0489 (17)	0.839 (4)	0.2697 (13)	0.020*
C1	0.3410 (2)	0.6464 (3)	0.49155 (12)	0.0167 (4)
C2	0.2827 (2)	0.4704 (3)	0.49730 (12)	0.0180 (5)
H2	0.2129	0.4231	0.4562	0.022*
C3	0.3320 (2)	0.3715 (3)	0.56527 (12)	0.0184 (5)
C4	0.4317 (2)	0.4407 (3)	0.62628 (12)	0.0196 (5)
C5	0.4909 (2)	0.6104 (3)	0.62154 (12)	0.0210 (5)
H5	0.5604	0.6558	0.6633	0.025*
C6	0.4440 (2)	0.7129 (3)	0.55232 (12)	0.0191 (5)
H6	0.4830	0.8305	0.5464	0.023*
C7	0.2959 (2)	0.7698 (3)	0.42134 (12)	0.0169 (4)
C8	0.1547 (2)	0.7454 (3)	0.37234 (12)	0.0179 (5)
H8	0.1346	0.6084	0.3635	0.022*
C9	0.0625 (2)	0.8330 (4)	0.41627 (13)	0.0259 (5)
H9A	0.0877	0.9641	0.4293	0.039*
H9B	0.0681	0.7622	0.4648	0.039*
H9C	−0.0273	0.8286	0.3829	0.039*
C10	0.2096 (2)	0.7604 (3)	0.24129 (13)	0.0225 (5)
H10A	0.2003	0.6217	0.2402	0.027*
H10B	0.3036	0.7909	0.2612	0.027*
C11	0.1584 (2)	0.8377 (4)	0.15924 (13)	0.0274 (5)
H11A	0.0665	0.8021	0.1386	0.041*
H11B	0.2095	0.7861	0.1252	0.041*
H11C	0.1659	0.9752	0.1606	0.041*
C12	0.3786 (2)	0.1531 (4)	0.66032 (13)	0.0242 (5)
H12A	0.4351	0.0459	0.6547	0.029*
H12B	0.3284	0.1172	0.6981	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0170 (3)	0.0162 (3)	0.0223 (3)	−0.00033 (18)	0.0019 (2)	−0.00118 (19)
O1	0.0224 (8)	0.0231 (9)	0.0218 (8)	−0.0049 (7)	0.0034 (6)	0.0024 (7)
O2	0.0295 (9)	0.0240 (9)	0.0216 (8)	−0.0058 (7)	0.0009 (7)	0.0069 (7)
O3	0.0235 (8)	0.0306 (10)	0.0167 (7)	−0.0002 (7)	0.0014 (6)	0.0059 (7)
N1	0.0170 (9)	0.0149 (9)	0.0167 (9)	−0.0009 (7)	0.0030 (7)	0.0003 (7)
C1	0.0162 (10)	0.0189 (11)	0.0158 (10)	0.0017 (8)	0.0058 (8)	0.0001 (8)
C2	0.0169 (10)	0.0212 (12)	0.0153 (9)	0.0002 (9)	0.0031 (8)	−0.0022 (8)
C3	0.0195 (10)	0.0189 (12)	0.0184 (10)	0.0000 (9)	0.0077 (8)	−0.0001 (9)
C4	0.0159 (10)	0.0289 (13)	0.0142 (9)	0.0053 (9)	0.0044 (8)	0.0011 (9)
C5	0.0154 (10)	0.0295 (13)	0.0169 (10)	−0.0017 (9)	0.0021 (8)	−0.0039 (9)
C6	0.0166 (10)	0.0220 (12)	0.0195 (10)	−0.0003 (9)	0.0062 (8)	−0.0023 (9)
C7	0.0192 (10)	0.0156 (11)	0.0166 (10)	−0.0009 (9)	0.0060 (8)	−0.0028 (8)
C8	0.0185 (10)	0.0183 (11)	0.0158 (10)	−0.0009 (9)	0.0023 (8)	0.0018 (8)
C9	0.0224 (11)	0.0355 (14)	0.0205 (11)	0.0033 (10)	0.0069 (9)	0.0019 (10)
C10	0.0261 (11)	0.0218 (12)	0.0219 (11)	0.0049 (10)	0.0104 (9)	0.0011 (9)
C11	0.0245 (11)	0.0376 (15)	0.0214 (11)	−0.0024 (11)	0.0087 (9)	0.0007 (10)
C12	0.0255 (11)	0.0267 (13)	0.0203 (11)	0.0018 (10)	0.0055 (9)	0.0044 (9)

Geometric parameters (Å, º)

O1—C7	1.215 (3)	C5—H5	0.9500
O2—C3	1.374 (3)	C6—H6	0.9500
O2—C12	1.434 (3)	C7—C8	1.529 (3)
O3—C4	1.370 (3)	C8—C9	1.532 (3)
O3—C12	1.445 (3)	C8—H8	1.0000
N1—C8	1.493 (3)	C9—H9A	0.9800
N1—C10	1.497 (3)	C9—H9B	0.9800
N1—H1A	0.896 (17)	C9—H9C	0.9800
N1—H1B	0.916 (16)	C10—C11	1.508 (3)
C1—C6	1.396 (3)	C10—H10A	0.9900
C1—C2	1.411 (3)	C10—H10B	0.9900
C1—C7	1.489 (3)	C11—H11A	0.9800
C2—C3	1.369 (3)	C11—H11B	0.9800
C2—H2	0.9500	C11—H11C	0.9800
C3—C4	1.385 (3)	C12—H12A	0.9900
C4—C5	1.372 (3)	C12—H12B	0.9900
C5—C6	1.396 (3)
C3—O2—C12	105.89 (17)	N1—C8—C9	109.00 (18)
C4—O3—C12	105.72 (16)	C7—C8—C9	109.27 (17)
C8—N1—C10	115.66 (17)	N1—C8—H8	109.6
C8—N1—H1A	107.9 (16)	C7—C8—H8	109.6
C10—N1—H1A	110.2 (16)	C9—C8—H8	109.6
C8—N1—H1B	107.9 (16)	C8—C9—H9A	109.5
C10—N1—H1B	107.9 (16)	C8—C9—H9B	109.5
H1A—N1—H1B	107 (2)	H9A—C9—H9B	109.5
C6—C1—C2	120.99 (19)	C8—C9—H9C	109.5
C6—C1—C7	116.9 (2)	H9A—C9—H9C	109.5
C2—C1—C7	122.07 (18)	H9B—C9—H9C	109.5
C3—C2—C1	116.42 (19)	N1—C10—C11	110.50 (18)
C3—C2—H2	121.8	N1—C10—H10A	109.6
C1—C2—H2	121.8	C11—C10—H10A	109.6
C2—C3—O2	127.7 (2)	N1—C10—H10B	109.6
C2—C3—C4	122.3 (2)	C11—C10—H10B	109.6
O2—C3—C4	109.94 (19)	H10A—C10—H10B	108.1
O3—C4—C5	127.78 (19)	C10—C11—H11A	109.5
O3—C4—C3	110.0 (2)	C10—C11—H11B	109.5
C5—C4—C3	122.2 (2)	H11A—C11—H11B	109.5
C4—C5—C6	116.66 (19)	C10—C11—H11C	109.5
C4—C5—H5	121.7	H11A—C11—H11C	109.5
C6—C5—H5	121.7	H11B—C11—H11C	109.5
C5—C6—C1	121.4 (2)	O2—C12—O3	107.52 (18)
C5—C6—H6	119.3	O2—C12—H12A	110.2
C1—C6—H6	119.3	O3—C12—H12A	110.2
O1—C7—C1	122.90 (19)	O2—C12—H12B	110.2
O1—C7—C8	119.89 (19)	O3—C12—H12B	110.2
C1—C7—C8	117.05 (18)	H12A—C12—H12B	108.5
N1—C8—C7	109.69 (17)
C6—C1—C2—C3	0.5 (3)	C2—C1—C6—C5	−1.6 (3)
C7—C1—C2—C3	−179.19 (19)	C7—C1—C6—C5	178.13 (19)
C1—C2—C3—O2	179.0 (2)	C6—C1—C7—O1	20.6 (3)
C1—C2—C3—C4	1.4 (3)	C2—C1—C7—O1	−159.7 (2)
C12—O2—C3—C2	176.9 (2)	C6—C1—C7—C8	−154.76 (19)
C12—O2—C3—C4	−5.2 (2)	C2—C1—C7—C8	24.9 (3)
C12—O3—C4—C5	−174.0 (2)	C10—N1—C8—C7	66.3 (2)
C12—O3—C4—C3	6.6 (2)	C10—N1—C8—C9	−174.07 (18)
C2—C3—C4—O3	177.09 (19)	O1—C7—C8—N1	18.5 (3)
O2—C3—C4—O3	−0.9 (2)	C1—C7—C8—N1	−165.97 (18)
C2—C3—C4—C5	−2.3 (3)	O1—C7—C8—C9	−100.9 (2)
O2—C3—C4—C5	179.69 (19)	C1—C7—C8—C9	74.6 (2)
O3—C4—C5—C6	−178.1 (2)	C8—N1—C10—C11	166.02 (19)
C3—C4—C5—C6	1.2 (3)	C3—O2—C12—O3	9.2 (2)
C4—C5—C6—C1	0.7 (3)	C4—O3—C12—O2	−9.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1	0.90 (2)	2.24 (2)	3.103 (2)	161 (2)

(V) Hydroxonium 1-(benzo[d][1,3]dioxol-5-yl)-2-(pyrrolidin-1-ium-1-yl)pentan-1-one dichloride

Crystal data

H7O3^+·C16H22NO3^+·2Cl^−	F(000) = 856
Mr = 402.30	Dx = 1.335 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 15.8084 (3) Å	Cell parameters from 9949 reflections
b = 11.4143 (2) Å	θ = 2.9–68.8°
c = 11.6289 (2) Å	µ = 3.18 mm^−1
β = 107.4200 (9)°	T = 100 K
V = 2002.10 (6) Å^3	Plate, colourless
Z = 4	0.46 × 0.35 × 0.06 mm

Data collection

Bruker SMART CCD APEXII area-detector diffractometer	3393 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.022
ϕ and ω scans	θmax = 68.6°, θmin = 2.9°
Absorption correction: numerical (SADABS; Sheldrick, 2008a)	h = −19→17
Tmin = 0.322, Tmax = 0.827	k = −13→12
18712 measured reflections	l = −13→13
3588 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.151	w = 1/[σ^2(Fo^2) + (0.0857P)^2 + 3.7517P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
3588 reflections	Δρmax = 1.53 e Å^−3
231 parameters	Δρmin = −0.39 e Å^−3
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2014), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (4)

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cl1	0.81575 (4)	0.44395 (5)	−0.20852 (5)	0.0120 (2)
Cl2	0.86519 (4)	0.92061 (5)	−0.22051 (6)	0.0205 (2)
O1	0.63452 (13)	0.21312 (18)	−0.17429 (17)	0.0235 (5)
O2	0.44639 (14)	0.09337 (19)	0.19210 (19)	0.0262 (5)
O3	0.32086 (14)	0.06743 (19)	0.0303 (2)	0.0285 (5)
O4	0.81206 (16)	0.6990 (2)	−0.1030 (2)	0.0345 (5)
H4A	0.8110	0.6260	−0.1280	0.052*
H4B	0.8220	0.7550	−0.1490	0.052*
O5	0.94897 (16)	0.5593 (2)	−0.3237 (2)	0.0368 (6)
H5A	0.9110	0.5290	−0.2900	0.055*
H5B	1.0008	0.5250	−0.3130	0.055*
O6	0.91195 (16)	0.7670 (2)	−0.3960 (2)	0.0350 (6)
H6A	0.8950	0.8080	−0.3430	0.053*
H6B	0.9170	0.6930	−0.3720	0.053*
H6C	0.8790	0.7890	−0.4684	0.053*
N1	0.78492 (16)	0.2702 (2)	−0.0051 (2)	0.0202 (5)
H1	0.777 (2)	0.315 (3)	−0.077 (3)	0.024*
C1	0.54542 (19)	0.1745 (2)	−0.0466 (3)	0.0204 (6)
C2	0.54399 (19)	0.1547 (2)	0.0725 (3)	0.0207 (6)
H2	0.5955	0.1642	0.1395	0.025*
C3	0.4645 (2)	0.1209 (2)	0.0869 (3)	0.0214 (6)
C4	0.38886 (19)	0.1052 (2)	−0.0103 (3)	0.0232 (6)
C5	0.3889 (2)	0.1230 (3)	−0.1275 (3)	0.0248 (6)
H5	0.3371	0.1118	−0.1937	0.030*
C6	0.4689 (2)	0.1582 (2)	−0.1437 (3)	0.0223 (6)
H6	0.4716	0.1716	−0.2232	0.027*
C7	0.62697 (19)	0.2129 (2)	−0.0727 (2)	0.0198 (6)
C8	0.70189 (18)	0.2617 (2)	0.0320 (2)	0.0198 (6)
H8	0.7127	0.2066	0.1018	0.024*
C9	0.86129 (19)	0.3256 (3)	0.0893 (3)	0.0257 (6)
H9A	0.8621	0.3002	0.1710	0.031*
H9B	0.8569	0.4121	0.0849	0.031*
C10	0.9444 (2)	0.2836 (3)	0.0605 (3)	0.0391 (9)
H10A	0.9894	0.2563	0.1347	0.047*
H10B	0.9702	0.3478	0.0247	0.047*
C11	0.9149 (2)	0.1824 (3)	−0.0295 (3)	0.0268 (7)
H11A	0.9163	0.2065	−0.1107	0.032*
H11B	0.9542	0.1137	−0.0033	0.032*
C12	0.8210 (2)	0.1536 (3)	−0.0307 (3)	0.0249 (6)
H12A	0.7859	0.1226	−0.1102	0.030*
H12B	0.8207	0.0954	0.0323	0.030*
C13	0.67422 (19)	0.3815 (2)	0.0697 (3)	0.0218 (6)
H13A	0.6253	0.3694	0.1052	0.026*
H13B	0.7249	0.4149	0.1333	0.026*
C14	0.6443 (2)	0.4703 (3)	−0.0325 (3)	0.0271 (7)
H14A	0.6923	0.4820	−0.0700	0.033*
H14B	0.5918	0.4395	−0.0951	0.033*
C15	0.6212 (3)	0.5872 (3)	0.0133 (3)	0.0373 (8)
H15A	0.5724	0.5762	0.0480	0.056*
H15B	0.6032	0.6429	−0.0537	0.056*
H15C	0.6732	0.6178	0.0752	0.056*
C16	0.3524 (2)	0.0827 (3)	0.1598 (3)	0.0283 (7)
H16A	0.3262	0.1540	0.1836	0.034*
H16B	0.3358	0.0144	0.2008	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0159 (3)	0.0109 (3)	0.0112 (3)	−0.0004 (2)	0.0070 (2)	0.0028 (2)
Cl2	0.0241 (4)	0.0166 (3)	0.0204 (4)	0.0029 (2)	0.0063 (3)	0.0004 (2)
O1	0.0276 (11)	0.0239 (10)	0.0191 (10)	0.0010 (8)	0.0072 (8)	0.0006 (8)
O2	0.0273 (11)	0.0281 (11)	0.0257 (11)	−0.0019 (9)	0.0117 (9)	−0.0020 (9)
O3	0.0242 (11)	0.0303 (12)	0.0313 (12)	−0.0039 (9)	0.0090 (9)	−0.0029 (9)
O4	0.0399 (13)	0.0301 (12)	0.0340 (13)	−0.0010 (10)	0.0121 (10)	0.0019 (10)
O5	0.0386 (13)	0.0309 (13)	0.0456 (14)	0.0031 (10)	0.0199 (11)	0.0048 (10)
O6	0.0423 (13)	0.0322 (12)	0.0321 (12)	0.0062 (10)	0.0135 (10)	0.0002 (10)
N1	0.0235 (12)	0.0185 (12)	0.0183 (12)	0.0019 (9)	0.0057 (10)	0.0003 (9)
C1	0.0260 (14)	0.0127 (13)	0.0220 (14)	0.0031 (11)	0.0064 (11)	−0.0007 (10)
C2	0.0226 (14)	0.0172 (13)	0.0212 (14)	0.0017 (11)	0.0047 (11)	−0.0011 (11)
C3	0.0288 (15)	0.0140 (13)	0.0221 (14)	0.0013 (11)	0.0087 (12)	−0.0011 (10)
C4	0.0232 (15)	0.0162 (14)	0.0304 (16)	0.0011 (11)	0.0083 (12)	−0.0010 (11)
C5	0.0251 (15)	0.0198 (14)	0.0252 (15)	0.0009 (11)	0.0011 (12)	−0.0002 (11)
C6	0.0279 (15)	0.0166 (13)	0.0207 (14)	0.0020 (11)	0.0048 (12)	0.0003 (11)
C7	0.0262 (15)	0.0140 (13)	0.0191 (14)	0.0044 (10)	0.0064 (11)	0.0013 (10)
C8	0.0236 (14)	0.0178 (14)	0.0187 (13)	0.0005 (11)	0.0074 (11)	0.0012 (11)
C9	0.0235 (15)	0.0282 (16)	0.0231 (15)	−0.0014 (12)	0.0036 (12)	−0.0054 (12)
C10	0.0243 (17)	0.045 (2)	0.044 (2)	0.0035 (14)	0.0033 (14)	−0.0170 (16)
C11	0.0263 (15)	0.0268 (16)	0.0263 (15)	0.0045 (12)	0.0064 (12)	−0.0031 (12)
C12	0.0281 (15)	0.0199 (14)	0.0276 (15)	0.0040 (12)	0.0096 (12)	−0.0016 (12)
C13	0.0230 (14)	0.0214 (14)	0.0213 (14)	−0.0003 (11)	0.0069 (11)	−0.0034 (11)
C14	0.0339 (17)	0.0207 (15)	0.0271 (16)	0.0044 (12)	0.0098 (13)	0.0005 (12)
C15	0.048 (2)	0.0250 (17)	0.0351 (19)	0.0094 (15)	0.0062 (16)	−0.0026 (14)
C16	0.0282 (16)	0.0285 (16)	0.0311 (17)	−0.0027 (12)	0.0135 (13)	−0.0039 (13)

Geometric parameters (Å, º)

O1—C7	1.222 (3)	C7—C8	1.528 (4)
O2—C3	1.374 (4)	C8—C13	1.539 (4)
O2—C16	1.424 (4)	C8—H8	1.0000
O3—C4	1.367 (4)	C9—C10	1.526 (4)
O3—C16	1.448 (4)	C9—H9A	0.9900
O4—H4A	0.8806	C9—H9B	0.9900
O4—H4B	0.8776	C10—C11	1.535 (4)
O5—H5A	0.8800	C10—H10A	0.9900
O5—H5B	0.8828	C10—H10B	0.9900
O6—H6A	0.8775	C11—C12	1.517 (4)
O6—H6B	0.8860	C11—H11A	0.9900
O6—H6C	0.8831	C11—H11B	0.9900
N1—C8	1.503 (4)	C12—H12A	0.9900
N1—C9	1.507 (4)	C12—H12B	0.9900
N1—C12	1.512 (4)	C13—C14	1.526 (4)
N1—H1	0.95 (4)	C13—H13A	0.9900
C1—C6	1.398 (4)	C13—H13B	0.9900
C1—C2	1.411 (4)	C14—C15	1.521 (4)
C1—C7	1.477 (4)	C14—H14A	0.9900
C2—C3	1.371 (4)	C14—H14B	0.9900
C2—H2	0.9500	C15—H15A	0.9800
C3—C4	1.389 (4)	C15—H15B	0.9800
C4—C5	1.379 (4)	C15—H15C	0.9800
C5—C6	1.393 (4)	C16—H16A	0.9900
C5—H5	0.9500	C16—H16B	0.9900
C6—H6	0.9500
C3—O2—C16	105.3 (2)	C10—C9—H9B	110.7
C4—O3—C16	105.0 (2)	H9A—C9—H9B	108.8
H4A—O4—H4B	118.5	C9—C10—C11	106.3 (3)
H5A—O5—H5B	119.4	C9—C10—H10A	110.5
H6A—O6—H6B	107.7	C11—C10—H10A	110.5
H6A—O6—H6C	107.5	C9—C10—H10B	110.5
H6B—O6—H6C	122.9	C11—C10—H10B	110.5
C8—N1—C9	113.3 (2)	H10A—C10—H10B	108.7
C8—N1—C12	114.4 (2)	C12—C11—C10	105.4 (2)
C9—N1—C12	104.3 (2)	C12—C11—H11A	110.7
C8—N1—H1	113 (2)	C10—C11—H11A	110.7
C9—N1—H1	106 (2)	C12—C11—H11B	110.7
C12—N1—H1	105 (2)	C10—C11—H11B	110.7
C6—C1—C2	120.5 (3)	H11A—C11—H11B	108.8
C6—C1—C7	118.1 (3)	N1—C12—C11	103.5 (2)
C2—C1—C7	121.4 (3)	N1—C12—H12A	111.1
C3—C2—C1	116.7 (3)	C11—C12—H12A	111.1
C3—C2—H2	121.6	N1—C12—H12B	111.1
C1—C2—H2	121.6	C11—C12—H12B	111.1
C2—C3—O2	128.0 (3)	H12A—C12—H12B	109.0
C2—C3—C4	122.3 (3)	C14—C13—C8	114.6 (2)
O2—C3—C4	109.6 (3)	C14—C13—H13A	108.6
O3—C4—C5	128.4 (3)	C8—C13—H13A	108.6
O3—C4—C3	109.5 (3)	C14—C13—H13B	108.6
C5—C4—C3	122.0 (3)	C8—C13—H13B	108.6
C4—C5—C6	116.5 (3)	H13A—C13—H13B	107.6
C4—C5—H5	121.8	C15—C14—C13	111.1 (3)
C6—C5—H5	121.8	C15—C14—H14A	109.4
C5—C6—C1	122.0 (3)	C13—C14—H14A	109.4
C5—C6—H6	119.0	C15—C14—H14B	109.4
C1—C6—H6	119.0	C13—C14—H14B	109.4
O1—C7—C1	122.9 (3)	H14A—C14—H14B	108.0
O1—C7—C8	119.5 (3)	C14—C15—H15A	109.5
C1—C7—C8	117.4 (2)	C14—C15—H15B	109.5
N1—C8—C7	109.3 (2)	H15A—C15—H15B	109.5
N1—C8—C13	111.8 (2)	C14—C15—H15C	109.5
C7—C8—C13	109.4 (2)	H15A—C15—H15C	109.5
N1—C8—H8	108.7	H15B—C15—H15C	109.5
C7—C8—H8	108.7	O2—C16—O3	107.0 (2)
C13—C8—H8	108.7	O2—C16—H16A	110.3
N1—C9—C10	105.2 (2)	O3—C16—H16A	110.3
N1—C9—H9A	110.7	O2—C16—H16B	110.3
C10—C9—H9A	110.7	O3—C16—H16B	110.3
N1—C9—H9B	110.7	H16A—C16—H16B	108.6
C6—C1—C2—C3	−0.9 (4)	C9—N1—C8—C7	175.9 (2)
C7—C1—C2—C3	179.0 (2)	C12—N1—C8—C7	−64.8 (3)
C1—C2—C3—O2	178.0 (3)	C9—N1—C8—C13	54.6 (3)
C1—C2—C3—C4	0.8 (4)	C12—N1—C8—C13	173.9 (2)
C16—O2—C3—C2	171.0 (3)	O1—C7—C8—N1	−16.7 (3)
C16—O2—C3—C4	−11.5 (3)	C1—C7—C8—N1	167.4 (2)
C16—O3—C4—C5	−171.0 (3)	O1—C7—C8—C13	106.1 (3)
C16—O3—C4—C3	11.3 (3)	C1—C7—C8—C13	−69.9 (3)
C2—C3—C4—O3	177.7 (3)	C8—N1—C9—C10	158.0 (3)
O2—C3—C4—O3	0.0 (3)	C12—N1—C9—C10	33.0 (3)
C2—C3—C4—C5	−0.2 (4)	N1—C9—C10—C11	−13.5 (4)
O2—C3—C4—C5	−177.9 (3)	C9—C10—C11—C12	−10.9 (4)
O3—C4—C5—C6	−177.8 (3)	C8—N1—C12—C11	−164.1 (2)
C3—C4—C5—C6	−0.3 (4)	C9—N1—C12—C11	−39.8 (3)
C4—C5—C6—C1	0.2 (4)	C10—C11—C12—N1	31.0 (3)
C2—C1—C6—C5	0.4 (4)	N1—C8—C13—C14	67.1 (3)
C7—C1—C6—C5	−179.5 (3)	C7—C8—C13—C14	−54.1 (3)
C6—C1—C7—O1	−11.9 (4)	C8—C13—C14—C15	−178.1 (3)
C2—C1—C7—O1	168.2 (3)	C3—O2—C16—O3	18.2 (3)
C6—C1—C7—C8	163.9 (2)	C4—O3—C16—O2	−18.2 (3)
C2—C1—C7—C8	−16.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.95 (4)	2.34 (4)	3.234 (2)	157 (3)
O4—H4A···Cl1^i	0.88	2.29	3.166 (2)	173
O4—H4B···Cl2	0.88	2.25	3.108 (2)	165
O5—H5A···Cl1^i	0.88	2.23	3.107 (2)	177
O5—H5B···Cl2^ii	0.88	2.36	3.240 (2)	176
O6—H6A···Cl2	0.88	2.07	2.948 (2)	173
O6—H6B···O5	0.89	1.65	2.525 (3)	168
O6—H6C···O4^iii	0.88	1.61	2.482 (3)	168

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