Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614025637/fg3326sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614025637/fg3326Isup7.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614025637/fg3326IIsup8.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614025637/fg3326IIIsup9.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614025637/fg3326IVsup10.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614025637/fg3326Vsup11.hkl |
CCDC references: 1035667; 1035666; 1035665; 1035664; 1035663
`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).
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.
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 Uiso(H) = 1.5Ueq(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 Uiso(H) = 1.2Ueq(C) or = 1.2Ueq(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.
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 HxOy+ (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.
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).
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) Å3 | Plate, colourless |
Z = 8 | 0.50 × 0.22 × 0.05 mm |
F(000) = 1377.4 |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0355P)2 + 1.1197P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00029 (6) |
C16H22NO3+·0.343(Br−)·0.657(Cl−) | V = 3128.5 (4) Å3 |
Mr = 327.06 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 7.0133 (5) Å | µ = 2.73 mm−1 |
b = 17.8399 (13) Å | T = 100 K |
c = 25.0044 (18) Å | 0.50 × 0.22 × 0.05 mm |
Bruker SMART CCD APEXII area-detector diffractometer | 2859 independent reflections |
Absorption correction: numerical (SADABS; Sheldrick, 2008a) | 2600 reflections with I > 2σ(I) |
Tmin = 0.400, Tmax = 0.896 | Rint = 0.037 |
27721 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.23 e Å−3 |
2859 reflections | Δρmin = −0.17 e Å−3 |
204 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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) |
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) Å3 | Needle, colourless |
Z = 4 | 0.43 × 0.18 × 0.06 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: mixed |
wR(F2) = 0.134 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.087P)2 + 3.9741P] where P = (Fo2 + 2Fc2)/3 |
2942 reflections | (Δ/σ)max = 0.001 |
194 parameters | Δρmax = 0.69 e Å−3 |
1 restraint | Δρmin = −1.24 e Å−3 |
C16H22NO3+·Br− | V = 1594.00 (5) Å3 |
Mr = 356.25 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 7.1280 (1) Å | µ = 3.60 mm−1 |
b = 21.3335 (5) Å | T = 293 K |
c = 10.5243 (2) Å | 0.43 × 0.18 × 0.06 mm |
β = 95.118 (1)° |
Bruker SMART CCD APEXII area-detector diffractometer | 2942 independent reflections |
Absorption correction: numerical (SADABS; Sheldrick, 2008a) | 2813 reflections with I > 2σ(I) |
Tmin = 0.307, Tmax = 0.813 | Rint = 0.021 |
14889 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 1 restraint |
wR(F2) = 0.134 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.69 e Å−3 |
2942 reflections | Δρmin = −1.24 e Å−3 |
194 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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) |
(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) Å3 | Rod, orange |
Z = 4 | 0.23 × 0.19 × 0.11 mm |
F(000) = 1184 |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0361P)2 + 26.5568P] where P = (Fo2 + 2Fc2)/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) |
(C16H22NO3)[AuCl4] | V = 2052.60 (13) Å3 |
Mr = 615.11 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 10.5046 (4) Å | µ = 18.40 mm−1 |
b = 11.1534 (4) Å | T = 100 K |
c = 17.5193 (6) Å | 0.23 × 0.19 × 0.11 mm |
Bruker SMART CCD APEXII area-detector diffractometer | 3554 independent reflections |
Absorption correction: numerical (SADABS; Sheldrick, 2008a) | 3479 reflections with I > 2σ(I) |
Tmin = 0.101, Tmax = 0.237 | Rint = 0.047 |
24150 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0361P)2 + 26.5568P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | Δρmax = 1.66 e Å−3 |
3554 reflections | Δρmin = −2.42 e Å−3 |
250 parameters | Absolute structure: Refined as an inversion twin. |
37 restraints | Absolute structure parameter: 0.45 (3) |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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) |
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) Å3 | Block, colourless |
Z = 4 | 0.33 × 0.31 × 0.15 mm |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.039 | Hydrogen site location: mixed |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.20 | w = 1/[σ2(Fo2) + (0.0393P)2 + 1.4462P] where P = (Fo2 + 2Fc2)/3 |
2253 reflections | (Δ/σ)max < 0.001 |
162 parameters | Δρmax = 0.36 e Å−3 |
2 restraints | Δρmin = −0.26 e Å−3 |
C12H16NO3+·Cl− | V = 1282.97 (9) Å3 |
Mr = 257.71 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 10.6159 (4) Å | µ = 2.62 mm−1 |
b = 7.1060 (3) Å | T = 100 K |
c = 17.6348 (6) Å | 0.33 × 0.31 × 0.15 mm |
β = 105.3310 (18)° |
Bruker SMART CCD APEXII area-detector diffractometer | 2253 independent reflections |
Absorption correction: numerical (SADABS; Sheldrick, 2008a) | 2097 reflections with I > 2σ(I) |
Tmin = 0.475, Tmax = 0.696 | Rint = 0.030 |
9602 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 2 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.20 | Δρmax = 0.36 e Å−3 |
2253 reflections | Δρmin = −0.26 e Å−3 |
162 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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) |
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) Å3 | Plate, colourless |
Z = 4 | 0.46 × 0.35 × 0.06 mm |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.151 | w = 1/[σ2(Fo2) + (0.0857P)2 + 3.7517P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0018 (4) |
H7O3+·C16H22NO3+·2Cl− | V = 2002.10 (6) Å3 |
Mr = 402.30 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 15.8084 (3) Å | µ = 3.18 mm−1 |
b = 11.4143 (2) Å | T = 100 K |
c = 11.6289 (2) Å | 0.46 × 0.35 × 0.06 mm |
β = 107.4200 (9)° |
Bruker SMART CCD APEXII area-detector diffractometer | 3588 independent reflections |
Absorption correction: numerical (SADABS; Sheldrick, 2008a) | 3393 reflections with I > 2σ(I) |
Tmin = 0.322, Tmax = 0.827 | Rint = 0.022 |
18712 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.151 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 1.53 e Å−3 |
3588 reflections | Δρmin = −0.39 e Å−3 |
231 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
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···Cl1i | 0.88 | 2.29 | 3.166 (2) | 173 |
O4—H4B···Cl2 | 0.88 | 2.25 | 3.108 (2) | 165 |
O5—H5A···Cl1i | 0.88 | 2.23 | 3.107 (2) | 177 |
O5—H5B···Cl2ii | 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···O4iii | 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. |
Experimental details
(I) | (II) | (III) | |
Crystal data | |||
Chemical formula | C16H22NO3+·0.343(Br−)·0.657(Cl−) | C16H22NO3+·Br− | (C16H22NO3)[AuCl4] |
Mr | 327.06 | 356.25 | 615.11 |
Crystal system, space group | Orthorhombic, Pbca | Monoclinic, P21/c | Orthorhombic, P212121 |
Temperature (K) | 100 | 293 | 100 |
a, b, c (Å) | 7.0133 (5), 17.8399 (13), 25.0044 (18) | 7.1280 (1), 21.3335 (5), 10.5243 (2) | 10.5046 (4), 11.1534 (4), 17.5193 (6) |
α, β, γ (°) | 90, 90, 90 | 90, 95.118 (1), 90 | 90, 90, 90 |
V (Å3) | 3128.5 (4) | 1594.00 (5) | 2052.60 (13) |
Z | 8 | 4 | 4 |
Radiation type | Cu Kα | Cu Kα | Cu Kα |
µ (mm−1) | 2.73 | 3.60 | 18.40 |
Crystal size (mm) | 0.50 × 0.22 × 0.05 | 0.43 × 0.18 × 0.06 | 0.23 × 0.19 × 0.11 |
Data collection | |||
Diffractometer | Bruker SMART CCD APEXII area-detector diffractometer | Bruker SMART CCD APEXII area-detector diffractometer | Bruker SMART CCD APEXII area-detector diffractometer |
Absorption correction | Numerical (SADABS; Sheldrick, 2008a) | Numerical (SADABS; Sheldrick, 2008a) | Numerical (SADABS; Sheldrick, 2008a) |
Tmin, Tmax | 0.400, 0.896 | 0.307, 0.813 | 0.101, 0.237 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27721, 2859, 2600 | 14889, 2942, 2813 | 24150, 3554, 3479 |
Rint | 0.037 | 0.021 | 0.047 |
(sin θ/λ)max (Å−1) | 0.610 | 0.609 | 0.608 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.066, 1.04 | 0.042, 0.134, 1.06 | 0.039, 0.096, 1.08 |
No. of reflections | 2859 | 2942 | 3554 |
No. of parameters | 204 | 194 | 250 |
No. of restraints | 0 | 1 | 37 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0355P)2 + 1.1197P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.087P)2 + 3.9741P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0361P)2 + 26.5568P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.23, −0.17 | 0.69, −1.24 | 1.66, −2.42 |
Absolute structure | ? | ? | Refined as an inversion twin. |
Absolute structure parameter | ? | ? | 0.45 (3) |
(IV) | (V) | |
Crystal data | ||
Chemical formula | C12H16NO3+·Cl− | H7O3+·C16H22NO3+·2Cl− |
Mr | 257.71 | 402.30 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 10.6159 (4), 7.1060 (3), 17.6348 (6) | 15.8084 (3), 11.4143 (2), 11.6289 (2) |
α, β, γ (°) | 90, 105.3310 (18), 90 | 90, 107.4200 (9), 90 |
V (Å3) | 1282.97 (9) | 2002.10 (6) |
Z | 4 | 4 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 2.62 | 3.18 |
Crystal size (mm) | 0.33 × 0.31 × 0.15 | 0.46 × 0.35 × 0.06 |
Data collection | ||
Diffractometer | Bruker SMART CCD APEXII area-detector diffractometer | Bruker SMART CCD APEXII area-detector diffractometer |
Absorption correction | Numerical (SADABS; Sheldrick, 2008a) | Numerical (SADABS; Sheldrick, 2008a) |
Tmin, Tmax | 0.475, 0.696 | 0.322, 0.827 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9602, 2253, 2097 | 18712, 3588, 3393 |
Rint | 0.030 | 0.022 |
(sin θ/λ)max (Å−1) | 0.610 | 0.604 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.107, 1.20 | 0.048, 0.151, 1.09 |
No. of reflections | 2253 | 3588 |
No. of parameters | 162 | 231 |
No. of restraints | 2 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
w = 1/[σ2(Fo2) + (0.0393P)2 + 1.4462P] where P = (Fo2 + 2Fc2)/3 | w = 1/[σ2(Fo2) + (0.0857P)2 + 3.7517P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.36, −0.26 | 1.53, −0.39 |
Absolute structure | ? | ? |
Absolute structure parameter | ? | ? |
Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008b), SHELXL2014 (Sheldrick, 2014).
(I) | (II) | (III) | (IV) | (V) | |
Phenyl ring versus Dioxo ring | 1.80 (9) | 2.40 (18) | 1.1 (6) | 2.04 (14) | 3.52 (9) |
Phenyl ring versus Ketone | 23.70 (8) | 17.73 (17) | 8.1 (6) | 23.58 (13) | 14.3 (1) |
Phenyl ring versus Pyrrole | 78.60 (5) | 88.94 (11) | 82.0 (4) | 62.15 (11) | |
Dioxo ring versus Ketone | 25.28 (8) | 17.26 (19) | 8.5 (6) | 25.35 (13) | 13.37 (11) |
Dioxo ring versus Pyrrole | 80.34 (5) | 89.85 (12) | 82.9 (4) | 59.18 (12) | |
Pyrrole versus Ketone | 62.37 (5) | 74.95 (12) | 75.0 (5) | 51.07 (13) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Br1 | 0.868 (19) | 2.34 (2) | 3.198 (2) | 171 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl4 | 0.920 (3) | 2.57 (7) | 3.41 (1) | 151 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl1 | 0.896 (17) | 2.243 (18) | 3.103 (2) | 161 (2) |
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···Cl1i | 0.88 | 2.29 | 3.166 (2) | 173 |
O4—H4B···Cl2 | 0.88 | 2.25 | 3.108 (2) | 165 |
O5—H5A···Cl1i | 0.88 | 2.23 | 3.107 (2) | 177 |
O5—H5B···Cl2ii | 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···O4iii | 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. |