Structural diversity in imidazolidinone organocatalysts: a synchrotron and computational study

(S)-1-(Methyl­amino­carbon­yl)-3-phenyl­propanaminium chloride (S2·HCl), C₁₀H₁₅N₂O⁺·Cl^-, crystallizes in the ortho­rhom­bic space group P2₁2₁2₁ with a single formula unit per asymmetric unit. (5R/S)-5-Benzyl-2,2,3-trimethyl-4-oxoimidazolidin-1-ium chloride (R3 and S3), C₁₃H₁₉N₂O⁺·Cl^-, crystallize in the same space group as S2·HCl but contain three symmetry-independent formula units. (R/S)-5-Benzyl-2,2,3-trimethyl-4-oxoimidazolidin-1-ium chloride monohydrate (R4 and S4), C₁₃H₁₉N₂O⁺·Cl^-·H₂O, crystallize in the space group P2₁ with a single formula unit per asymmetric unit. Calculations at the B3LYP/6-31G(d,p) and B3LYP/6-311G(d,p) levels of the conformational energies of the cation in R3, S3, R4 and S4 indicate that the ideal gas-phase global energy minimum conformation is not observed in the solid state. Rather, the effects of hydrogen-bonding and van der Waals inter­actions in the crystal structure cause the mol­ecules to adopt higher-energy conformations, which correspond to local minima in the mol­ecular potential energy surface.

S1. Comment

A number of research groups have reported on the utility of chiral imidazolidinone catalysts for a range of enantioselective organic reactions (Ahrendt et al., 2000; Wilson et al., 2005; Paras & MacMillan, 2001; Jen et al., 2000; Marigo et al., 2005; Kunz & MacMillan, 2005; Beeson & MacMillan, 2005; Brochu et al., 2004). Several reviews of the field of organocatalysis exist (Almaşi et al., 2007; Bolm et al., 2005; Gaunt et al., 2007; Tsogoeva 2007; List 2006). Enantiomeric excesses greater than 90% are regularly achieved in relatively high yielding reactions that are difficult to accomplish by other means. However, there are to date very few structural studies of these materials, and no reports of their stability to storage or recrystallization. Both of these factors are expected to be highly relevant to possible use of the materials in both industrial and laboratory settings.

The catalyst studied in the current work is a typical example of the class (Ahrendt et al., 2000), is commercially available, and has been described as `an inexpensive, bench-stable solid that is readily handled by experimentalists or automated systems' (Beeson & MacMillan, 2005). We therefore selected this compound for a full structural characterization, which is of interest both to confirm the reported molecular structure of this material, and with a view to rationalizing its solid-state properties, including particle morphology and flow, solubility, stability etc. Synchrotron radiation was employed in order to gain the best quality structural information from these weakly scattering materials and to ensure that our study was not biased in favour of solid forms which readily form single crystals. A simplified reaction scheme is given in Scheme 1.

S2.HCl [(S)-phenylalanine methylamide hydrochloride] adopts the orthorhombic spacegroup P2₁2₁2₁ with a single formula unit per asymmetric unit (Fig. 1a). All chemically intuitive hydrogen bonding opportunities are satisfied in the solid state (Fig. 2a). Sheets of hydrogen bonds are formed, which lie parallel to the ab plane. The chloride ion is hydrogen-bonded by three protonated amine groups [N16···Cl1 = 3.094 (2), 3.149 (2) and 3.166 (2) Å], and the carbonyl group of the amide unit is hydrogen bonded to the amide H atom on an adjacent molecule [N11···O10 = 3.018 (3) Å]. The hydrophobic (phenyl) and hydrophilic (amide) fragments of the molecule form layers, which are segregated along the c axis. Solid-state packing forces appear to have a slight influence on the molecular conformation; comparison of the observed molecular conformation with one computed using a gas-phase molecular mechanics model shows no unusual features, the two conformations being broadly similar. The primary differences arise because of a change in the C6—C7—C8—C9 torsion angle from 98.15° in the gas phase (calculated as described in the Experimental section) to 54.65° in the solid-state, which is presumably driven by a combination of crystal packing (optimal space filling) requirements and intermolecular hydrogen bonding of the amide group.

R3 and S3 [5(R/S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one hydrochloride] both crystallize in the orthorhombic space group P2₁2₁2₁ with three formula units per asymmetric unit (S3 is shown in Fig. 1b). The three organic molecules adopt different but related conformations which differ primarily as a result of changes in the orientation of the imidazolidinone fragment with respect to the phenyl ring via C—C bond rotation. These differences in conformation do not affect the hydrogen-bonding topology, with all three organic cations forming two N—H···Cl hydrogen bonds from the protonated N atom to the free chloride ion (Fig. 2b). Neither the carbonyl nor the nitrogen of the amide group are involved in classical hydrogen bonding for any of the three distinct molecules, which is in contrast to the extensive hydrogen bonding observed for the precursor S2.HCl. Two of the three independent formula units are linked to each other by hydrogen bonding through Cl1 and Cl2 via N—H···Cl interactions and thereby form a chain of hydrogen bonds which runs parallel to the a axis. The third symmetry-independent formula unit again forms N—H···Cl hydrogen bonds to create a chain that runs parallel to both the a axis and the other hydrogen-bonding chain, but in this case the chain comprises only a single symmetry-independent molecule and a single symmetry-independent chloride ion (Cl1). The hydrophilic sections of the structure (Cl^- ions and the polar parts of the organic cation) are layered in the ac plane and are separated by the hydrophobic phenyl rings. As expected, no significant differences exist between the crystal packing of the (R) and (S) isomers.

The presence of three formula units with different molecular conformations in the asymmetric unit is curious, and could result from either different minima on the molecular energy surface or distortions away from the same minimum caused by differences in packing forces experienced by the three independent molecules in the unit cell. To distinguish between these possibilities, we have performed calculations designed to elucidate the gas-phase conformers and their relative energies. R3 and S3 have two torsional degrees of freedom, which we label ϕ (torsion angle C6—C7—C8—C9) and θ (torsion angle C5—C6—C7—C8). Initial low-level calculations (using the molecular mechanics model Tripos 5.2) indicate that three distinct conformational energy minima exist in the gas phase (Fig. 3). The three minima were then re-optimized at higher levels of theory for more reliable relative energies, revealing large energy differences between the conformations: the relative energies are 0, +10.67 [+11.29], +32.57 [+33.95] kJ mol^-1 for conformations i, ii and iii, respectively, at the B3LYP/6–31 G(d,p) [B3LYP/6–311 G(d,p)] levels. The good quantitative agreement between the two methods indicates that the effects of basis set superposition error on the relative conformational energies is small, while the stability of the most folded conformation i might even be underestimated owing to the known poor treatment of nonbonded interactions in density functional theory calculations (van Mourik et al., 2006). As typical energy differences between polymorphs are of the order of 1–10 kJ mol^-1 (Bernstein, 2002), we might only expect the lowest energy conformation to be observed in the crystal structure. However, it is clear from Fig. 3 that two molecules (A and C) adopt conformations related to the intermediate-energy calculated conformation ii, while molecule (B) is within the potential energy well of the highest-energy calculated conformation iii, although significantly distorted away from the minimum. It therefore appears that in order to optimize the lattice energy, the three molecules avoid the lowest-energy, folded gas-phase conformation in favor of the two open conformations. The conformational energy penalty of at least 18 kJ mol^-1 (2 × 11 kJ mol^-1 for A and C, 33 kJ mol^-1 for B) is presumably compensated by the formation of hydrogen bonds and van der Waals interactions in the crystal.

Both R4 and S4 [5(R/S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one hydrochloride hydrate] crystallize in the noncentrosymmetric monoclinic space group P2₁ with a single formula unit per asymmetric unit (S4 is shown in Fig. 1c). The conformation of the cation (θ = 109.3°, ϕ = 173.4°) corresponds most closely with minimum ii (Fig. 3), and it therefore appears that, as with R3 and S3, intermolecular factors including hydrogen bonding and van der Waals interactions outweigh intramolecular ones in determining the conformation of the cation in the solid state. Overall the hydrogen bonding leads to the formation of tapes which run parallel to the b axis (Fig. 2c). Again, the hydrophobic and hydrophilic parts of the structure are segregated into chains which follow the hydrogen-bonding topology. Again, no unexpected differences exist between the crystal packing of the (R) and (S) isomers.

In conclusion, computational and experimental studies indicate that intermolecular rather than intramolecular forces are primarily responsible for the molecular conformations observed in the solid state for this class of compounds.

Related literature

For related literature, see: Ahrendt et al. (2000); Almaşi et al. (2007); Amos (1995); Beeson & MacMillan (2005); Bernstein (2002); Bolm et al. (2005); Brochu et al. (2004); Gaunt et al. (2007); Hassinen & Peräkylä (2001); Jen et al. (2000); Kunz & MacMillan (2005); List (2006); Marigo et al. (2005); Mourik et al. (2006); Paras & MacMillan (2001); Tsogoeva (2007); Wilson et al. (2005).

S2. Experimental

For the synthesis of the catalyst, 5(S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one was synthesized from commercially available (S)-phenylalanine methylester hydrochloride according to the literature method described by Ahrendt et al. (2000). Treatment of (S)-phenylalanine methylester hydrochloride with ethanolic methylamine furnished the intermediate (S)-phenylalanine N-methyl amide hydrochloride, which was not isolated, but heated to reflux in MeOH and acetone with catalytic para-toluenesulfonic acid (p-TSA). The cyclized (S)-imidazolidinone product was precipitated as the HCl salt and recrystallized from 2-propanol to yield a microcrystalline white needle-like material, which was identical to that previously characterized. The (R)-enantiomer was prepared in an identical manner starting from commercially available (R)-phenylalanine methylamide hydrochloride. This material displayed identical ¹H and ¹³C NMR spectra to the (S)-enantiomer, and had an equal but opposite optical rotation value, as expected. A simplified reaction scheme is shown in the Comment section.

Initial attempts to grow large crystals by slow evaporation (several months, 277 K) from CHCl₃ were successful in this aim, but crystallographic characterization indicated that ring opening of the imidazolidinone had occurred to yield (R/S)-phenylalanine methylamide hydrochloride. As the crystal structure of this material had not been reported, a full data set was collected on the (S) isomer and is reported here. Crystals of 5(R/S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one hydrochloride were grown by rapid evaporation (ca 2 days, ambient temperature) from CHCl₃. Samples of 5(R/S)-5-benzyl-2,2,3-trimethylimidazolidin-4-one hydrochloride hydrate were crystallized from 2-propanol as a microcrystalline powder and correspond to the `raw' reagent described in the synthesis; these were subject to standard benchtop storage conditions for several months after crystallization.

Single crystals were selected, mounted at the end of two-stage glass fibres and studied at 150 K on station 9.8 or station 16.2 SMX of the UK Synchrotron Radiation Source, Daresbury. Routine data collection involved three series of ω scans. Data were corrected for beam decay and absorption using a method based on equivalents. Further details can be found in the relevant section of the CIF that accompanies this paper.

Computational studies were performed to investigate the conformational energy landscape of the molecular cations. For both protonated (R/S)-phenylalanine methylamide and for the imidazolidinone cation, initial calculations were performed using a simple molecular mechanics model (Tripos 5.2) as implemented in Ghemical (Hassinen & Peräkylä, 2001). For the imidazolidinone cation, for which the potential energy landscape was relatively complex, the three local minima located in the initial molecular mechanics search were investigated at a higher level of theory. The three molecular mechanics energy minima were energy minimized using both B3LYP/6–31 G(d,p) and B3LYP/6–311 G(d,p) levels of theory, giving refined gas phase molecular structures and their relative energies. All density functional theory calculations were performed using the program CADPAC (Amos, 1995).

Computing details

Data collection: APEX2 (Bruker, 2004) for S2.HCl, R3, S3, R4; APEXII (Bruker, 2004) for S4. Cell refinement: APEX2 (Bruker, 2004) for S2.HCl, R3, S3, R4; APEXII (Bruker, 2004) for S4. Data reduction: APEX2 (Bruker, 2004) for S2.HCl, R3, S3, R4; APEXII (Bruker, 2004) for S4. For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: WinGX (Version 1.64; Farrugia, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. : The asymmetric units of (a) S2.HCl, (b) S3 and (c) S4. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. : Hydrogen-bonding patterns observed in (a) S2.HCl (the hydrogen-bonded sheet is viewed side-on for clarity), (b) S3 (only one of the three chains is shown for clarity) and (c) S4. (Colour key for the onoline version of the journal: carbon grey, hydrogen white, nitrogen blue, oxygen red, chlorine green.)
	Fig. 3. : Calculated (Tripos 5.2) conformational energy landscape for the (S)-5-benzyl-2,2,3-trimethyl-4-oxoimidazolidin-1-ium cation, and energy-minimized calculated conformations. Numbers refer to calculated conformations, letters to those observed experimentally. See text and Fig. 1 for further details.

(S2.HCl) (S)-1-(methylaminocarbonyl)-3-phenylpropanaminium chloride

Crystal data

C10H15N2O^+·Cl^−	F(000) = 456
Mr = 214.69	Dx = 1.303 Mg m^−3
Orthorhombic, P212121	Synchrotron radiation, λ = 0.69040 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2000 reflections
a = 4.9758 (7) Å	θ = 2.4–24.5°
b = 8.6213 (13) Å	µ = 0.32 mm^−1
c = 25.521 (4) Å	T = 150 K
V = 1094.8 (3) Å^3	Block, colourless
Z = 4	0.15 × 0.07 × 0.07 mm

Data collection

Bruker D8 diffractometer	3619 independent reflections
Radiation source: Daresbury SRS, Station 16.2SMX	2971 reflections with I > 2σ(I)
Silicon 111 monochromator	Rint = 0.091
ω rotation with narrow frame scans	θmax = 31.2°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −7→7
Tmin = 0.953, Tmax = 0.978	k = −12→12
12758 measured reflections	l = −36→36

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.157	w = 1/[σ^2(Fo^2) + (0.0882P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
3619 reflections	Δρmax = 0.58 e Å^−3
141 parameters	Δρmin = −0.57 e Å^−3
4 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (9)

Special details

Experimental. A correction to account for beam decay and absorption was applied using SADABS. The ratio of max to min apparent transmission was 0.748

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl1	0.80225 (12)	0.77857 (7)	0.21217 (2)	0.02442 (15)
C1	0.5003 (6)	0.4375 (3)	0.03794 (10)	0.0265 (5)
H1	0.6370	0.3934	0.0578	0.032*
C2	0.4683 (6)	0.3934 (3)	−0.01397 (11)	0.0309 (6)
H2	0.5831	0.3205	−0.0288	0.037*
C3	0.2642 (6)	0.4586 (3)	−0.04355 (10)	0.0290 (6)
H3	0.2419	0.4292	−0.0783	0.035*
C4	0.0933 (6)	0.5672 (3)	−0.02155 (10)	0.0306 (6)
H4	−0.0431	0.6112	−0.0416	0.037*
C5	0.1262 (6)	0.6104 (3)	0.03054 (10)	0.0266 (5)
H5	0.0099	0.6826	0.0454	0.032*
C6	0.3310 (5)	0.5468 (3)	0.06072 (9)	0.0220 (4)
C7	0.3747 (6)	0.5994 (3)	0.11668 (9)	0.0246 (5)
H7A	0.2988	0.7023	0.1209	0.029*
H7B	0.5663	0.6067	0.1232	0.029*
C8	0.2494 (5)	0.4913 (3)	0.15748 (9)	0.0210 (5)
H8	0.0559	0.4830	0.1509	0.025*
C9	0.3736 (5)	0.3295 (3)	0.15676 (9)	0.0205 (4)
O10	0.6195 (4)	0.3128 (2)	0.16136 (8)	0.0290 (4)
N11	0.1991 (4)	0.2140 (2)	0.15128 (8)	0.0211 (4)
H11	0.031 (4)	0.236 (4)	0.1547 (11)	0.036 (4)*
C12	0.2767 (6)	0.0524 (3)	0.15529 (10)	0.0293 (6)
H12A	0.1576	−0.0001	0.1790	0.044*
H12B	0.4575	0.0455	0.1682	0.044*
H12C	0.2664	0.0048	0.1213	0.044*
N16	0.2938 (4)	0.5585 (2)	0.21067 (8)	0.0218 (4)
H16A	0.176 (6)	0.632 (3)	0.2181 (12)	0.036 (4)*
H16B	0.282 (7)	0.491 (3)	0.2370 (9)	0.036 (4)*
H16C	0.451 (5)	0.605 (4)	0.2140 (13)	0.036 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0236 (3)	0.0211 (2)	0.0285 (3)	0.0000 (2)	0.0011 (2)	−0.0047 (2)
C1	0.0216 (12)	0.0296 (13)	0.0284 (12)	0.0018 (11)	−0.0031 (10)	0.0009 (10)
C2	0.0295 (15)	0.0334 (13)	0.0297 (12)	0.0031 (11)	−0.0001 (11)	−0.0020 (11)
C3	0.0276 (14)	0.0347 (13)	0.0246 (11)	−0.0021 (11)	−0.0046 (9)	0.0001 (9)
C4	0.0298 (14)	0.0312 (13)	0.0309 (13)	0.0002 (11)	−0.0053 (11)	0.0048 (10)
C5	0.0253 (13)	0.0233 (11)	0.0312 (12)	0.0030 (10)	−0.0021 (10)	0.0001 (10)
C6	0.0220 (12)	0.0200 (9)	0.0238 (10)	−0.0030 (9)	−0.0015 (9)	0.0024 (8)
C7	0.0295 (13)	0.0173 (10)	0.0269 (11)	−0.0031 (9)	0.0006 (10)	0.0019 (9)
C8	0.0189 (12)	0.0185 (9)	0.0256 (10)	0.0000 (8)	0.0001 (8)	−0.0001 (8)
C9	0.0204 (11)	0.0191 (10)	0.0220 (10)	0.0017 (9)	0.0016 (8)	0.0021 (8)
O10	0.0176 (8)	0.0256 (9)	0.0440 (11)	0.0024 (7)	−0.0012 (8)	−0.0014 (7)
N11	0.0195 (9)	0.0175 (8)	0.0263 (9)	−0.0007 (9)	0.0025 (8)	−0.0016 (7)
C12	0.0324 (14)	0.0170 (10)	0.0385 (13)	0.0000 (10)	0.0042 (11)	0.0021 (9)
N16	0.0210 (9)	0.0192 (8)	0.0252 (9)	−0.0008 (8)	0.0037 (9)	0.0004 (7)

Geometric parameters (Å, º)

C1—C2	1.388 (4)	C7—H7B	0.9700
C1—C6	1.391 (4)	C8—N16	1.492 (3)
C1—H1	0.9300	C8—C9	1.526 (3)
C2—C3	1.384 (4)	C8—H8	0.9800
C2—H2	0.9300	C9—O10	1.238 (3)
C3—C4	1.384 (4)	C9—N11	1.328 (3)
C3—H3	0.9300	N11—C12	1.449 (3)
C4—C5	1.390 (4)	N11—H11	0.864 (18)
C4—H4	0.9300	C12—H12A	0.9600
C5—C6	1.390 (3)	C12—H12B	0.9600
C5—H5	0.9300	C12—H12C	0.9600
C6—C7	1.514 (3)	N16—H16A	0.883 (18)
C7—C8	1.530 (3)	N16—H16B	0.892 (17)
C7—H7A	0.9700	N16—H16C	0.880 (18)
C2—C1—C6	121.0 (2)	N16—C8—C9	107.81 (18)
C2—C1—H1	119.5	N16—C8—C7	108.84 (19)
C6—C1—H1	119.5	C9—C8—C7	112.6 (2)
C3—C2—C1	119.6 (3)	N16—C8—H8	109.2
C3—C2—H2	120.2	C9—C8—H8	109.2
C1—C2—H2	120.2	C7—C8—H8	109.2
C4—C3—C2	120.3 (2)	O10—C9—N11	124.7 (2)
C4—C3—H3	119.9	O10—C9—C8	120.3 (2)
C2—C3—H3	119.9	N11—C9—C8	115.0 (2)
C3—C4—C5	119.8 (3)	C9—N11—C12	122.6 (2)
C3—C4—H4	120.1	C9—N11—H11	117 (2)
C5—C4—H4	120.1	C12—N11—H11	118 (2)
C6—C5—C4	120.7 (2)	N11—C12—H12A	109.5
C6—C5—H5	119.7	N11—C12—H12B	109.5
C4—C5—H5	119.7	H12A—C12—H12B	109.5
C5—C6—C1	118.7 (2)	N11—C12—H12C	109.5
C5—C6—C7	120.6 (2)	H12A—C12—H12C	109.5
C1—C6—C7	120.7 (2)	H12B—C12—H12C	109.5
C6—C7—C8	113.7 (2)	C8—N16—H16A	112 (2)
C6—C7—H7A	108.8	C8—N16—H16B	115 (2)
C8—C7—H7A	108.8	H16A—N16—H16B	105 (3)
C6—C7—H7B	108.8	C8—N16—H16C	113 (2)
C8—C7—H7B	108.8	H16A—N16—H16C	104 (3)
H7A—C7—H7B	107.7	H16B—N16—H16C	106 (3)

(R3) (R)-5-benzyl-2,2,3-trimethyl-4-oxoimidazolidin-1-ium chloride

Crystal data

C13H19N2O^+·Cl^−	F(000) = 1632
Mr = 254.75	Dx = 1.221 Mg m^−3
Orthorhombic, P212121	Synchrotron radiation, λ = 0.69040 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2939 reflections
a = 7.1167 (14) Å	θ = 2.6–23.5°
b = 19.237 (4) Å	µ = 0.26 mm^−1
c = 30.370 (6) Å	T = 150 K
V = 4157.7 (14) Å^3	Block, colourless
Z = 12	0.1 × 0.08 × 0.04 mm

Data collection

Bruker D8 diffractometer	9772 independent reflections
Radiation source: Daresbury SRS, Station 16.2SMX	7354 reflections with I > 2σ(I)
Silicon 111 monochromator	Rint = 0.071
ω rotation with narrow frame scans	θmax = 27.2°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→8
Tmin = 0.974, Tmax = 0.990	k = −25→24
24370 measured reflections	l = −37→40

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.131	w = 1/[σ^2(Fo^2) + (0.0431P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max = 0.001
9772 reflections	Δρmax = 0.28 e Å^−3
488 parameters	Δρmin = −0.23 e Å^−3
6 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (6)

Special details

Experimental. A correction to account for beam decay and absorption was applied using SADABS. The ratio of max to min apparent transmission was 0.692.

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Ffrom the least squares refinement, Flack x parameter = 0.0036 e.s.d. 0.0555

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

	x	y	z	Uiso*/Ueq
Cl1	0.46650 (11)	0.67659 (4)	0.20932 (2)	0.03596 (17)
Cl2	0.03772 (12)	0.29717 (4)	0.03881 (2)	0.03702 (17)
Cl3	0.95538 (11)	0.74670 (4)	0.12677 (2)	0.03563 (17)
C1	0.7744 (6)	0.46455 (15)	0.01218 (11)	0.0456 (9)
H1	0.8945	0.4544	0.0242	0.055*
C2	0.7600 (7)	0.50897 (18)	−0.02362 (13)	0.0585 (11)
H2	0.8698	0.5290	−0.0360	0.070*
C3	0.5861 (7)	0.52401 (18)	−0.04115 (12)	0.0638 (12)
H3	0.5757	0.5548	−0.0655	0.077*
C4	0.4280 (7)	0.49429 (17)	−0.02337 (11)	0.0564 (11)
H4	0.3083	0.5044	−0.0356	0.068*
C5	0.4418 (6)	0.44972 (16)	0.01234 (10)	0.0473 (9)
H5	0.3316	0.4293	0.0244	0.057*
C6	0.6155 (5)	0.43491 (14)	0.03055 (10)	0.0376 (8)
C7	0.6356 (5)	0.39431 (14)	0.07324 (10)	0.0353 (7)
H7A	0.5985	0.4254	0.0977	0.042*
H7B	0.7705	0.3834	0.0772	0.042*
C8	0.5259 (5)	0.32682 (13)	0.07814 (8)	0.0293 (6)
H8	0.3928	0.3337	0.0685	0.035*
C9	0.5317 (4)	0.30392 (14)	0.12622 (9)	0.0311 (6)
O10	0.5073 (3)	0.34214 (10)	0.15770 (6)	0.0437 (6)
N11	0.5659 (4)	0.23550 (11)	0.12752 (7)	0.0308 (5)
C12	0.5528 (5)	0.19533 (16)	0.16773 (9)	0.0390 (7)
H12A	0.5590	0.2266	0.1931	0.058*
H12B	0.6572	0.1622	0.1691	0.058*
H12C	0.4333	0.1700	0.1682	0.058*
C13	0.5733 (4)	0.20211 (14)	0.08390 (9)	0.0304 (7)
C14	0.3854 (5)	0.16930 (16)	0.07276 (10)	0.0414 (8)
H14A	0.3562	0.1330	0.0944	0.062*
H14B	0.3915	0.1487	0.0433	0.062*
H14C	0.2871	0.2050	0.0734	0.062*
C15	0.7356 (5)	0.15277 (16)	0.07957 (10)	0.0405 (8)
H15A	0.8506	0.1754	0.0901	0.061*
H15B	0.7510	0.1396	0.0486	0.061*
H15C	0.7112	0.1111	0.0972	0.061*
N16	0.6093 (4)	0.26534 (12)	0.05525 (8)	0.0291 (5)
H16A	0.730 (3)	0.2719 (17)	0.0534 (11)	0.041 (4)*
H16B	0.576 (5)	0.2568 (15)	0.0282 (7)	0.041 (4)*
C21	1.1491 (5)	0.52093 (16)	0.20431 (11)	0.0439 (8)
H21	1.2265	0.5252	0.2297	0.053*
C22	1.2151 (6)	0.48585 (16)	0.16804 (11)	0.0482 (9)
H22	1.3371	0.4658	0.1684	0.058*
C23	1.1041 (6)	0.47985 (15)	0.13141 (11)	0.0471 (9)
H23	1.1482	0.4545	0.1066	0.057*
C24	0.9307 (6)	0.51003 (16)	0.13026 (11)	0.0500 (9)
H24	0.8562	0.5072	0.1044	0.060*
C25	0.8636 (5)	0.54468 (15)	0.16681 (10)	0.0414 (8)
H25	0.7420	0.5650	0.1660	0.050*
C26	0.9706 (5)	0.55017 (13)	0.20433 (9)	0.0328 (6)
C27	0.8962 (4)	0.58805 (14)	0.24435 (9)	0.0329 (7)
H27A	0.9219	0.5596	0.2709	0.039*
H27B	0.7583	0.5929	0.2416	0.039*
C28	0.9821 (4)	0.66006 (13)	0.25076 (9)	0.0298 (6)
H28	1.1179	0.6586	0.2423	0.036*
C29	0.9646 (4)	0.68746 (14)	0.29762 (9)	0.0304 (6)
O30	0.9865 (3)	0.65260 (10)	0.33076 (6)	0.0404 (5)
N31	0.9272 (4)	0.75559 (12)	0.29557 (7)	0.0308 (5)
C32	0.9406 (5)	0.80102 (16)	0.33398 (9)	0.0403 (8)
H32A	0.9329	0.7730	0.3609	0.060*
H32B	0.8371	0.8346	0.3335	0.060*
H32C	1.0607	0.8259	0.3333	0.060*
C33	0.9131 (4)	0.78357 (14)	0.25062 (9)	0.0305 (7)
C34	1.0940 (5)	0.81854 (16)	0.23651 (11)	0.0412 (8)
H34A	1.1203	0.8578	0.2561	0.062*
H34B	1.0811	0.8354	0.2062	0.062*
H34C	1.1975	0.7850	0.2381	0.062*
C35	0.7443 (5)	0.82979 (16)	0.24437 (10)	0.0385 (7)
H35A	0.6327	0.8069	0.2565	0.058*
H35B	0.7256	0.8386	0.2129	0.058*
H35C	0.7649	0.8740	0.2597	0.058*
N36	0.8859 (4)	0.71663 (13)	0.22517 (8)	0.0293 (5)
H36A	0.935 (5)	0.7194 (16)	0.1989 (7)	0.041 (4)*
H36B	0.765 (3)	0.7066 (17)	0.2250 (11)	0.041 (4)*
C41	0.6783 (5)	0.91208 (17)	0.12749 (11)	0.0409 (7)
H41	0.7310	0.8807	0.1067	0.049*
C42	0.7844 (5)	0.96729 (16)	0.14272 (10)	0.0419 (8)
H42	0.9094	0.9731	0.1324	0.050*
C43	0.7130 (5)	1.01334 (16)	0.17222 (11)	0.0450 (8)
H43	0.7867	1.0511	0.1826	0.054*
C44	0.5314 (6)	1.00407 (17)	0.18681 (13)	0.0597 (10)
H44	0.4794	1.0361	0.2073	0.072*
C45	0.4241 (5)	0.94923 (16)	0.17223 (12)	0.0487 (9)
H45	0.2995	0.9435	0.1828	0.058*
C46	0.4971 (4)	0.90207 (14)	0.14203 (9)	0.0321 (7)
C47	0.3752 (4)	0.84086 (15)	0.12911 (11)	0.0375 (7)
H47A	0.3152	0.8223	0.1561	0.045*
H47B	0.2737	0.8581	0.1097	0.045*
C48	0.4734 (4)	0.78160 (13)	0.10597 (9)	0.0295 (6)
H48	0.6035	0.7772	0.1181	0.035*
C49	0.4846 (4)	0.78635 (14)	0.05643 (9)	0.0300 (6)
O50	0.5207 (3)	0.83844 (10)	0.03534 (7)	0.0404 (5)
N51	0.4441 (4)	0.72297 (12)	0.03941 (7)	0.0320 (6)
C52	0.4636 (6)	0.70676 (17)	−0.00714 (9)	0.0450 (8)
H52A	0.4556	0.7497	−0.0244	0.068*
H52B	0.3628	0.6751	−0.0161	0.068*
H52C	0.5856	0.6846	−0.0123	0.068*
C53	0.4100 (4)	0.66876 (14)	0.07240 (9)	0.0294 (6)
C54	0.2379 (5)	0.62580 (15)	0.06236 (10)	0.0367 (7)
H54A	0.1332	0.6566	0.0548	0.055*
H54B	0.2044	0.5981	0.0883	0.055*
H54C	0.2643	0.5948	0.0375	0.055*
C55	0.5835 (5)	0.62492 (16)	0.08050 (10)	0.0404 (8)
H55A	0.6200	0.6016	0.0531	0.061*
H55B	0.5562	0.5900	0.1031	0.061*
H55C	0.6865	0.6548	0.0905	0.061*
N56	0.3730 (4)	0.71421 (12)	0.11235 (8)	0.0276 (5)
H56A	0.411 (4)	0.6939 (14)	0.1374 (7)	0.041 (4)*
H56B	0.254 (3)	0.7225 (16)	0.1151 (11)	0.041 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0272 (4)	0.0518 (4)	0.0288 (3)	−0.0009 (3)	−0.0003 (3)	0.0016 (3)
Cl2	0.0310 (4)	0.0531 (4)	0.0270 (3)	0.0020 (4)	0.0009 (3)	−0.0046 (3)
Cl3	0.0247 (3)	0.0557 (4)	0.0265 (3)	−0.0007 (4)	0.0009 (3)	0.0008 (3)
C1	0.059 (2)	0.0333 (16)	0.0443 (19)	−0.0063 (16)	0.0077 (18)	−0.0072 (14)
C2	0.084 (3)	0.0417 (19)	0.050 (2)	−0.018 (2)	0.013 (2)	−0.0044 (17)
C3	0.107 (4)	0.0432 (19)	0.0409 (19)	−0.017 (2)	−0.008 (2)	0.0042 (16)
C4	0.081 (3)	0.0426 (18)	0.0457 (19)	−0.009 (2)	−0.020 (2)	0.0036 (15)
C5	0.065 (3)	0.0361 (16)	0.0408 (18)	−0.0084 (18)	−0.0093 (18)	−0.0002 (13)
C6	0.057 (2)	0.0226 (13)	0.0328 (16)	−0.0054 (14)	0.0020 (16)	−0.0085 (11)
C7	0.0360 (18)	0.0343 (15)	0.0355 (16)	0.0001 (13)	0.0001 (14)	−0.0054 (12)
C8	0.0308 (15)	0.0293 (13)	0.0277 (13)	0.0007 (13)	−0.0006 (13)	−0.0030 (10)
C9	0.0289 (15)	0.0352 (14)	0.0292 (13)	0.0017 (13)	0.0014 (14)	−0.0019 (11)
O10	0.0555 (17)	0.0432 (11)	0.0324 (11)	0.0009 (11)	0.0096 (11)	−0.0089 (9)
N11	0.0343 (15)	0.0345 (12)	0.0236 (11)	0.0040 (11)	0.0013 (11)	−0.0021 (9)
C12	0.047 (2)	0.0460 (16)	0.0244 (14)	0.0049 (16)	−0.0004 (14)	0.0041 (12)
C13	0.0381 (19)	0.0295 (13)	0.0236 (13)	0.0024 (12)	−0.0016 (13)	0.0002 (11)
C14	0.047 (2)	0.0392 (16)	0.0382 (17)	−0.0080 (16)	−0.0041 (15)	0.0017 (13)
C15	0.053 (2)	0.0396 (16)	0.0288 (16)	0.0134 (16)	0.0028 (15)	−0.0028 (13)
N16	0.0302 (14)	0.0329 (12)	0.0242 (12)	0.0002 (11)	−0.0013 (11)	−0.0021 (9)
C21	0.050 (2)	0.0419 (17)	0.0403 (18)	0.0053 (16)	−0.0040 (17)	0.0007 (14)
C22	0.056 (2)	0.0375 (17)	0.051 (2)	0.0090 (17)	0.0115 (18)	0.0010 (15)
C23	0.076 (3)	0.0262 (15)	0.0389 (18)	−0.0030 (16)	0.0091 (19)	−0.0045 (13)
C24	0.071 (3)	0.0408 (17)	0.0382 (17)	−0.0108 (18)	−0.0092 (19)	−0.0041 (14)
C25	0.046 (2)	0.0382 (16)	0.0400 (18)	−0.0033 (15)	−0.0046 (16)	0.0008 (14)
C26	0.0428 (17)	0.0248 (12)	0.0307 (14)	−0.0050 (13)	−0.0010 (15)	0.0002 (11)
C27	0.0325 (17)	0.0348 (15)	0.0314 (15)	−0.0010 (13)	0.0014 (13)	0.0014 (12)
C28	0.0286 (16)	0.0322 (14)	0.0287 (13)	0.0035 (12)	0.0004 (12)	−0.0004 (11)
C29	0.0255 (14)	0.0394 (15)	0.0262 (13)	0.0046 (13)	0.0008 (13)	−0.0022 (11)
O30	0.0445 (15)	0.0467 (11)	0.0300 (10)	0.0116 (11)	−0.0034 (10)	0.0045 (9)
N31	0.0329 (15)	0.0376 (12)	0.0219 (11)	0.0041 (11)	−0.0015 (10)	−0.0022 (9)
C32	0.048 (2)	0.0441 (16)	0.0289 (15)	0.0060 (16)	−0.0036 (15)	−0.0099 (12)
C33	0.0322 (18)	0.0325 (14)	0.0269 (14)	0.0013 (12)	0.0028 (12)	−0.0041 (11)
C34	0.041 (2)	0.0436 (17)	0.0387 (17)	−0.0109 (15)	0.0086 (15)	−0.0086 (14)
C35	0.047 (2)	0.0367 (16)	0.0317 (16)	0.0067 (15)	−0.0011 (14)	0.0058 (13)
N36	0.0280 (14)	0.0362 (13)	0.0236 (11)	−0.0022 (11)	0.0021 (11)	−0.0001 (10)
C41	0.0406 (19)	0.0456 (18)	0.0365 (17)	−0.0084 (15)	0.0090 (16)	−0.0055 (14)
C42	0.043 (2)	0.0448 (18)	0.0380 (17)	−0.0148 (15)	0.0021 (15)	0.0043 (14)
C43	0.051 (2)	0.0307 (16)	0.053 (2)	−0.0063 (16)	−0.0079 (18)	−0.0005 (15)
C44	0.058 (3)	0.0424 (19)	0.078 (3)	−0.0053 (19)	0.017 (2)	−0.0264 (18)
C45	0.042 (2)	0.0409 (17)	0.063 (2)	−0.0044 (15)	0.0148 (18)	−0.0093 (16)
C46	0.0354 (19)	0.0287 (13)	0.0321 (14)	−0.0010 (12)	−0.0002 (13)	0.0030 (11)
C47	0.0325 (17)	0.0378 (16)	0.0422 (17)	−0.0061 (14)	0.0073 (15)	−0.0073 (13)
C48	0.0234 (15)	0.0353 (14)	0.0297 (13)	−0.0021 (13)	0.0002 (13)	−0.0011 (11)
C49	0.0248 (17)	0.0345 (14)	0.0306 (14)	−0.0005 (12)	0.0003 (12)	0.0019 (11)
O50	0.0455 (14)	0.0366 (10)	0.0390 (11)	−0.0050 (10)	0.0076 (11)	0.0073 (9)
N51	0.0350 (15)	0.0361 (12)	0.0249 (11)	−0.0053 (11)	0.0019 (11)	0.0007 (9)
C52	0.054 (2)	0.0530 (18)	0.0279 (14)	−0.0115 (18)	0.0053 (17)	−0.0044 (13)
C53	0.0299 (16)	0.0324 (14)	0.0260 (14)	−0.0002 (12)	−0.0013 (12)	0.0003 (11)
C54	0.0379 (19)	0.0340 (15)	0.0383 (17)	−0.0061 (14)	−0.0032 (14)	0.0033 (13)
C55	0.038 (2)	0.0415 (16)	0.0417 (17)	0.0099 (15)	−0.0024 (15)	−0.0028 (14)
N56	0.0241 (13)	0.0320 (12)	0.0267 (12)	0.0012 (10)	0.0004 (11)	0.0040 (9)

Geometric parameters (Å, º)

C1—C6	1.384 (5)	C29—O30	1.219 (3)
C1—C2	1.387 (5)	C29—N31	1.339 (3)
C1—H1	0.9500	N31—C32	1.461 (3)
C2—C3	1.377 (6)	N31—C33	1.471 (3)
C2—H2	0.9500	C32—H32A	0.9800
C3—C4	1.373 (6)	C32—H32B	0.9800
C3—H3	0.9500	C32—H32C	0.9800
C4—C5	1.386 (4)	C33—C35	1.506 (4)
C4—H4	0.9500	C33—C34	1.514 (4)
C5—C6	1.384 (5)	C33—N36	1.514 (4)
C5—H5	0.9500	C34—H34A	0.9800
C6—C7	1.520 (4)	C34—H34B	0.9800
C7—C8	1.522 (4)	C34—H34C	0.9800
C7—H7A	0.9900	C35—H35A	0.9800
C7—H7B	0.9900	C35—H35B	0.9800
C8—N16	1.495 (3)	C35—H35C	0.9800
C8—C9	1.526 (4)	N36—H36A	0.872 (17)
C8—H8	1.0000	N36—H36B	0.883 (18)
C9—O10	1.219 (3)	C41—C46	1.376 (4)
C9—N11	1.339 (3)	C41—C42	1.383 (4)
N11—C12	1.448 (3)	C41—H41	0.9500
N11—C13	1.473 (3)	C42—C43	1.359 (5)
C12—H12A	0.9800	C42—H42	0.9500
C12—H12B	0.9800	C43—C44	1.378 (5)
C12—H12C	0.9800	C43—H43	0.9500
C13—C15	1.501 (4)	C44—C45	1.375 (5)
C13—C14	1.517 (4)	C44—H44	0.9500
C13—N16	1.517 (4)	C45—C46	1.391 (4)
C14—H14A	0.9800	C45—H45	0.9500
C14—H14B	0.9800	C46—C47	1.514 (4)
C14—H14C	0.9800	C47—C48	1.510 (4)
C15—H15A	0.9800	C47—H47A	0.9900
C15—H15B	0.9800	C47—H47B	0.9900
C15—H15C	0.9800	C48—N56	1.493 (4)
N16—H16A	0.867 (18)	C48—C49	1.510 (4)
N16—H16B	0.872 (17)	C48—H48	1.0000
C21—C22	1.375 (4)	C49—O50	1.217 (3)
C21—C26	1.390 (5)	C49—N51	1.355 (3)
C21—H21	0.9500	N51—C52	1.454 (3)
C22—C23	1.369 (5)	N51—C53	1.466 (3)
C22—H22	0.9500	C52—H52A	0.9800
C23—C24	1.365 (5)	C52—H52B	0.9800
C23—H23	0.9500	C52—H52C	0.9800
C24—C25	1.380 (5)	C53—C54	1.509 (4)
C24—H24	0.9500	C53—C55	1.515 (4)
C25—C26	1.374 (4)	C53—N56	1.518 (4)
C25—H25	0.9500	C54—H54A	0.9800
C26—C27	1.513 (4)	C54—H54B	0.9800
C27—C28	1.527 (4)	C54—H54C	0.9800
C27—H27A	0.9900	C55—H55A	0.9800
C27—H27B	0.9900	C55—H55B	0.9800
C28—N36	1.502 (4)	C55—H55C	0.9800
C28—C29	1.523 (4)	N56—H56A	0.895 (17)
C28—H28	1.0000	N56—H56B	0.868 (18)
C6—C1—C2	120.6 (4)	C29—N31—C32	122.4 (2)
C6—C1—H1	119.7	C29—N31—C33	114.5 (2)
C2—C1—H1	119.7	C32—N31—C33	121.8 (2)
C3—C2—C1	119.9 (4)	N31—C32—H32A	109.5
C3—C2—H2	120.0	N31—C32—H32B	109.5
C1—C2—H2	120.0	H32A—C32—H32B	109.5
C4—C3—C2	119.8 (3)	N31—C32—H32C	109.5
C4—C3—H3	120.1	H32A—C32—H32C	109.5
C2—C3—H3	120.1	H32B—C32—H32C	109.5
C3—C4—C5	120.5 (4)	N31—C33—C35	112.8 (2)
C3—C4—H4	119.7	N31—C33—C34	111.6 (2)
C5—C4—H4	119.7	C35—C33—C34	112.3 (2)
C6—C5—C4	120.2 (4)	N31—C33—N36	99.9 (2)
C6—C5—H5	119.9	C35—C33—N36	109.6 (2)
C4—C5—H5	119.9	C34—C33—N36	110.0 (2)
C1—C6—C5	118.9 (3)	C33—C34—H34A	109.5
C1—C6—C7	118.6 (3)	C33—C34—H34B	109.5
C5—C6—C7	122.0 (3)	H34A—C34—H34B	109.5
C6—C7—C8	118.3 (2)	C33—C34—H34C	109.5
C6—C7—H7A	107.7	H34A—C34—H34C	109.5
C8—C7—H7A	107.7	H34B—C34—H34C	109.5
C6—C7—H7B	107.7	C33—C35—H35A	109.5
C8—C7—H7B	107.7	C33—C35—H35B	109.5
H7A—C7—H7B	107.1	H35A—C35—H35B	109.5
N16—C8—C7	115.2 (2)	C33—C35—H35C	109.5
N16—C8—C9	101.9 (2)	H35A—C35—H35C	109.5
C7—C8—C9	109.0 (2)	H35B—C35—H35C	109.5
N16—C8—H8	110.1	C28—N36—C33	107.1 (2)
C7—C8—H8	110.1	C28—N36—H36A	110 (2)
C9—C8—H8	110.1	C33—N36—H36A	111 (2)
O10—C9—N11	126.6 (3)	C28—N36—H36B	107 (2)
O10—C9—C8	124.9 (2)	C33—N36—H36B	108 (2)
N11—C9—C8	108.5 (2)	H36A—N36—H36B	113 (3)
C9—N11—C12	122.5 (2)	C46—C41—C42	120.8 (3)
C9—N11—C13	114.1 (2)	C46—C41—H41	119.6
C12—N11—C13	121.9 (2)	C42—C41—H41	119.6
N11—C12—H12A	109.5	C43—C42—C41	121.1 (3)
N11—C12—H12B	109.5	C43—C42—H42	119.4
H12A—C12—H12B	109.5	C41—C42—H42	119.4
N11—C12—H12C	109.5	C42—C43—C44	118.6 (3)
H12A—C12—H12C	109.5	C42—C43—H43	120.7
H12B—C12—H12C	109.5	C44—C43—H43	120.7
N11—C13—C15	112.5 (2)	C45—C44—C43	121.1 (3)
N11—C13—C14	110.5 (2)	C45—C44—H44	119.5
C15—C13—C14	113.3 (2)	C43—C44—H44	119.5
N11—C13—N16	99.9 (2)	C44—C45—C46	120.4 (3)
C15—C13—N16	109.1 (2)	C44—C45—H45	119.8
C14—C13—N16	110.8 (2)	C46—C45—H45	119.8
C13—C14—H14A	109.5	C41—C46—C45	118.0 (3)
C13—C14—H14B	109.5	C41—C46—C47	124.2 (3)
H14A—C14—H14B	109.5	C45—C46—C47	117.7 (3)
C13—C14—H14C	109.5	C48—C47—C46	116.3 (3)
H14A—C14—H14C	109.5	C48—C47—H47A	108.2
H14B—C14—H14C	109.5	C46—C47—H47A	108.2
C13—C15—H15A	109.5	C48—C47—H47B	108.2
C13—C15—H15B	109.5	C46—C47—H47B	108.2
H15A—C15—H15B	109.5	H47A—C47—H47B	107.4
C13—C15—H15C	109.5	N56—C48—C49	102.0 (2)
H15A—C15—H15C	109.5	N56—C48—C47	112.0 (2)
H15B—C15—H15C	109.5	C49—C48—C47	116.3 (2)
C8—N16—C13	107.5 (2)	N56—C48—H48	108.8
C8—N16—H16A	108 (2)	C49—C48—H48	108.8
C13—N16—H16A	109 (2)	C47—C48—H48	108.8
C8—N16—H16B	119 (2)	O50—C49—N51	125.8 (3)
C13—N16—H16B	110 (2)	O50—C49—C48	125.8 (3)
H16A—N16—H16B	104 (3)	N51—C49—C48	108.3 (2)
C22—C21—C26	120.7 (3)	C49—N51—C52	122.9 (2)
C22—C21—H21	119.6	C49—N51—C53	114.5 (2)
C26—C21—H21	119.6	C52—N51—C53	121.8 (2)
C23—C22—C21	119.7 (4)	N51—C52—H52A	109.5
C23—C22—H22	120.1	N51—C52—H52B	109.5
C21—C22—H22	120.1	H52A—C52—H52B	109.5
C24—C23—C22	120.4 (3)	N51—C52—H52C	109.5
C24—C23—H23	119.8	H52A—C52—H52C	109.5
C22—C23—H23	119.8	H52B—C52—H52C	109.5
C23—C24—C25	119.9 (3)	N51—C53—C54	112.7 (2)
C23—C24—H24	120.1	N51—C53—C55	111.8 (2)
C25—C24—H24	120.1	C54—C53—C55	112.9 (2)
C26—C25—C24	120.8 (3)	N51—C53—N56	99.5 (2)
C26—C25—H25	119.6	C54—C53—N56	109.6 (2)
C24—C25—H25	119.6	C55—C53—N56	109.4 (2)
C25—C26—C21	118.4 (3)	C53—C54—H54A	109.5
C25—C26—C27	120.6 (3)	C53—C54—H54B	109.5
C21—C26—C27	121.0 (3)	H54A—C54—H54B	109.5
C26—C27—C28	113.6 (2)	C53—C54—H54C	109.5
C26—C27—H27A	108.9	H54A—C54—H54C	109.5
C28—C27—H27A	108.9	H54B—C54—H54C	109.5
C26—C27—H27B	108.9	C53—C55—H55A	109.5
C28—C27—H27B	108.9	C53—C55—H55B	109.5
H27A—C27—H27B	107.7	H55A—C55—H55B	109.5
N36—C28—C29	101.3 (2)	C53—C55—H55C	109.5
N36—C28—C27	114.1 (2)	H55A—C55—H55C	109.5
C29—C28—C27	113.6 (2)	H55B—C55—H55C	109.5
N36—C28—H28	109.2	C48—N56—C53	108.3 (2)
C29—C28—H28	109.2	C48—N56—H56A	110 (2)
C27—C28—H28	109.2	C53—N56—H56A	112 (2)
O30—C29—N31	127.0 (2)	C48—N56—H56B	109 (2)
O30—C29—C28	124.8 (2)	C53—N56—H56B	111 (2)
N31—C29—C28	108.2 (2)	H56A—N56—H56B	107 (3)

(S3) (S)-5-benzyl-2,2,3-trimethyl-4-oxoimidazolidin-1-ium chloride

Crystal data

C13H19N2O^+·Cl^−	F(000) = 1632
Mr = 254.75	Dx = 1.220 Mg m^−3
Orthorhombic, P212121	Synchrotron radiation, λ = 0.69040 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3066 reflections
a = 7.123 (1) Å	θ = 2.7–23.6°
b = 19.232 (3) Å	µ = 0.26 mm^−1
c = 30.384 (4) Å	T = 150 K
V = 4162.3 (10) Å^3	Block, colourless
Z = 12	0.2 × 0.06 × 0.04 mm

Data collection

Bruker D8 diffractometer	13171 independent reflections
Radiation source: Daresbury SRS, Station 16.2SMX	8896 reflections with I > 2σ(I)
Silicon 111 monochromator	Rint = 0.126
ω rotation with narrow frame scans	θmax = 30.0°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→10
Tmin = 0.949, Tmax = 0.990	k = −27→27
48955 measured reflections	l = −43→43

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.071	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.171	w = 1/[σ^2(Fo^2) + (0.0126P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
13171 reflections	Δρmax = 0.46 e Å^−3
488 parameters	Δρmin = −0.32 e Å^−3
6 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.09 (6)

Special details

Experimental. A correction to account for beam decay and absorption was applied using SADABS. The ratio of max to min apparent transmission was 0.739.

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl1	0.53380 (11)	0.32275 (4)	0.79074 (2)	0.03396 (16)
Cl2	0.96381 (13)	0.70284 (4)	0.96122 (2)	0.03500 (17)
Cl3	0.04468 (11)	0.25258 (4)	0.87330 (2)	0.03409 (17)
H56A	0.600 (5)	0.3032 (16)	0.8612 (7)	0.036 (4)*
H56B	0.746 (3)	0.2736 (17)	0.8869 (11)	0.036 (4)*
C1	0.2282 (6)	0.53542 (17)	0.98777 (11)	0.0430 (8)
H1	0.1076	0.5456	0.9760	0.052*
C2	0.2455 (7)	0.4905 (2)	1.02394 (13)	0.0560 (11)
H2	0.1364	0.4703	1.0367	0.067*
C3	0.4205 (8)	0.47542 (19)	1.04115 (12)	0.0622 (13)
H3	0.4319	0.4443	1.0653	0.075*
C4	0.5774 (7)	0.50544 (18)	1.02342 (12)	0.0539 (11)
H4	0.6975	0.4958	1.0357	0.065*
C5	0.5619 (6)	0.54990 (17)	0.98758 (11)	0.0422 (8)
H5	0.6716	0.5703	0.9753	0.051*
C6	0.3866 (5)	0.56480 (15)	0.96944 (10)	0.0349 (7)
C7	0.3667 (5)	0.60562 (15)	0.92724 (10)	0.0318 (7)
H7A	0.2317	0.6164	0.9233	0.038*
H7B	0.4037	0.5747	0.9027	0.038*
C8	0.4754 (5)	0.67320 (14)	0.92214 (9)	0.0276 (6)
H8	0.6082	0.6665	0.9320	0.033*
C9	0.4718 (4)	0.69630 (15)	0.87405 (9)	0.0306 (6)
O10	0.4953 (4)	0.65743 (11)	0.84275 (7)	0.0407 (6)
N11	0.4343 (4)	0.76402 (12)	0.87275 (8)	0.0293 (5)
C12	0.4476 (5)	0.80409 (18)	0.83224 (9)	0.0381 (8)
H12A	0.4357	0.7728	0.8069	0.057*
H12B	0.5695	0.8277	0.8311	0.057*
H12C	0.3466	0.8387	0.8314	0.057*
C13	0.4273 (5)	0.79772 (15)	0.91599 (9)	0.0292 (6)
C14	0.6154 (5)	0.83084 (18)	0.92734 (11)	0.0407 (8)
H14A	0.6439	0.8675	0.9060	0.061*
H14B	0.7143	0.7954	0.9264	0.061*
H14C	0.6093	0.8509	0.9570	0.061*
C15	0.2643 (5)	0.84718 (17)	0.92033 (10)	0.0393 (8)
H15A	0.1487	0.8240	0.9107	0.059*
H15B	0.2868	0.8882	0.9019	0.059*
H15C	0.2514	0.8615	0.9512	0.059*
N16	0.3922 (4)	0.73451 (13)	0.94478 (8)	0.0275 (5)
H16A	0.272 (3)	0.7298 (18)	0.9466 (11)	0.036 (4)*
H16B	0.421 (5)	0.7438 (16)	0.9719 (7)	0.036 (4)*
C21	−0.1484 (5)	0.47847 (18)	0.79588 (11)	0.0409 (8)
H21	−0.2260	0.4742	0.7706	0.049*
C22	−0.2146 (6)	0.51350 (18)	0.83248 (12)	0.0475 (9)
H22	−0.3371	0.5331	0.8322	0.057*
C23	−0.1043 (6)	0.52008 (17)	0.86910 (12)	0.0478 (10)
H23	−0.1486	0.5455	0.8938	0.057*
C24	0.0712 (6)	0.48976 (18)	0.87013 (11)	0.0472 (9)
H24	0.1459	0.4925	0.8960	0.057*
C25	0.1383 (5)	0.45512 (17)	0.83318 (10)	0.0388 (8)
H25	0.2603	0.4351	0.8337	0.047*
C26	0.0300 (5)	0.44944 (14)	0.79575 (9)	0.0321 (6)
C27	0.1026 (5)	0.41159 (15)	0.75596 (9)	0.0321 (7)
H27A	0.2407	0.4071	0.7585	0.039*
H27B	0.0759	0.4400	0.7295	0.039*
C28	0.0186 (4)	0.33942 (14)	0.74938 (9)	0.0274 (6)
H28	−0.1171	0.3406	0.7579	0.033*
C29	0.0348 (5)	0.31232 (15)	0.70267 (9)	0.0302 (6)
O30	0.0128 (4)	0.34709 (12)	0.66958 (7)	0.0404 (6)
N31	0.0729 (4)	0.24400 (13)	0.70432 (7)	0.0289 (5)
C32	0.0578 (6)	0.19817 (18)	0.66614 (10)	0.0395 (8)
H32A	0.0584	0.2261	0.6391	0.059*
H32B	−0.0597	0.1717	0.6679	0.059*
H32C	0.1644	0.1660	0.6658	0.059*
C33	0.0869 (4)	0.21537 (15)	0.74915 (9)	0.0277 (6)
C34	−0.0947 (5)	0.18070 (18)	0.76337 (11)	0.0390 (8)
H34A	−0.1230	0.1420	0.7434	0.059*
H34B	−0.1973	0.2146	0.7624	0.059*
H34C	−0.0810	0.1630	0.7935	0.059*
C35	0.2567 (5)	0.16925 (17)	0.75526 (10)	0.0360 (7)
H35A	0.3698	0.1942	0.7458	0.054*
H35B	0.2420	0.1270	0.7375	0.054*
H35C	0.2686	0.1566	0.7864	0.054*
N36	0.1146 (4)	0.28279 (13)	0.77481 (8)	0.0265 (5)
H36A	0.080 (5)	0.2829 (17)	0.8024 (6)	0.036 (4)*
H36B	0.236 (3)	0.2922 (18)	0.7749 (11)	0.036 (4)*
C41	0.3222 (5)	0.08721 (18)	0.87222 (11)	0.0381 (7)
H41	0.2695	0.1186	0.8930	0.046*
C42	0.2153 (5)	0.03171 (17)	0.85695 (11)	0.0392 (8)
H42	0.0906	0.0256	0.8674	0.047*
C43	0.2876 (6)	−0.01399 (18)	0.82713 (12)	0.0434 (8)
H43	0.2141	−0.0518	0.8167	0.052*
C44	0.4680 (6)	−0.00467 (18)	0.81235 (14)	0.0553 (10)
H44	0.5198	−0.0362	0.7915	0.066*
C45	0.5744 (6)	0.05022 (18)	0.82757 (12)	0.0463 (9)
H45	0.6994	0.0558	0.8172	0.056*
C46	0.5030 (4)	0.09731 (15)	0.85769 (9)	0.0297 (7)
C47	0.6257 (4)	0.15824 (16)	0.87117 (11)	0.0345 (7)
H47A	0.7253	0.1407	0.8910	0.041*
H47B	0.6883	0.1766	0.8445	0.041*
C48	0.5267 (4)	0.21795 (14)	0.89394 (9)	0.0260 (6)
H48	0.3965	0.2223	0.8818	0.031*
C49	0.5162 (4)	0.21312 (15)	0.94358 (9)	0.0286 (6)
O50	0.4780 (4)	0.16091 (11)	0.96445 (7)	0.0391 (5)
N51	0.5560 (4)	0.27634 (13)	0.96047 (8)	0.0307 (6)
C52	0.5372 (6)	0.29278 (18)	1.00678 (9)	0.0425 (8)
H52A	0.5478	0.2501	1.0242	0.064*
H52B	0.4143	0.3142	1.0121	0.064*
H52C	0.6367	0.3252	1.0155	0.064*
C53	0.5908 (4)	0.33055 (15)	0.92720 (9)	0.0291 (6)
C54	0.7626 (5)	0.37387 (16)	0.93720 (10)	0.0350 (7)
H54A	0.8699	0.3432	0.9427	0.053*
H54B	0.7388	0.4025	0.9633	0.053*
H54C	0.7903	0.4041	0.9120	0.053*
C55	0.4180 (5)	0.37474 (18)	0.91928 (11)	0.0388 (8)
H55A	0.3822	0.3980	0.9467	0.058*
H55B	0.3145	0.3451	0.9093	0.058*
H55C	0.4456	0.4097	0.8967	0.058*
N56	0.6276 (4)	0.28507 (13)	0.88767 (8)	0.0268 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0249 (3)	0.0500 (4)	0.0270 (3)	−0.0013 (3)	0.0001 (3)	0.0018 (3)
Cl2	0.0294 (4)	0.0500 (4)	0.0256 (3)	0.0017 (4)	0.0005 (3)	−0.0043 (3)
Cl3	0.0227 (3)	0.0542 (4)	0.0255 (3)	−0.0003 (4)	0.0005 (3)	0.0001 (3)
C1	0.055 (2)	0.0341 (17)	0.0397 (18)	−0.0077 (17)	0.0087 (17)	−0.0059 (14)
C2	0.083 (3)	0.041 (2)	0.044 (2)	−0.018 (2)	0.017 (2)	−0.0034 (17)
C3	0.111 (4)	0.0370 (19)	0.0382 (19)	−0.015 (2)	−0.008 (2)	0.0027 (16)
C4	0.075 (3)	0.0396 (19)	0.047 (2)	−0.008 (2)	−0.020 (2)	0.0037 (16)
C5	0.053 (2)	0.0363 (17)	0.0377 (17)	−0.0046 (17)	−0.0051 (17)	−0.0020 (14)
C6	0.052 (2)	0.0253 (14)	0.0276 (15)	−0.0024 (14)	0.0008 (14)	−0.0065 (11)
C7	0.0313 (17)	0.0304 (15)	0.0337 (15)	0.0000 (13)	0.0005 (13)	−0.0079 (12)
C8	0.0277 (14)	0.0297 (13)	0.0254 (13)	0.0038 (13)	−0.0010 (12)	−0.0041 (11)
C9	0.0274 (14)	0.0369 (15)	0.0274 (13)	0.0029 (13)	0.0029 (13)	−0.0030 (12)
O10	0.0510 (16)	0.0409 (12)	0.0303 (10)	0.0025 (11)	0.0109 (10)	−0.0086 (9)
N11	0.0337 (14)	0.0302 (12)	0.0239 (11)	0.0045 (11)	0.0008 (11)	−0.0002 (9)
C12	0.044 (2)	0.0492 (18)	0.0208 (13)	0.0078 (17)	0.0034 (14)	0.0036 (13)
C13	0.0391 (19)	0.0285 (14)	0.0201 (12)	0.0009 (13)	0.0010 (12)	−0.0001 (11)
C14	0.046 (2)	0.0391 (18)	0.0367 (17)	−0.0075 (16)	−0.0032 (15)	0.0015 (14)
C15	0.051 (2)	0.0377 (17)	0.0293 (16)	0.0155 (16)	0.0048 (15)	−0.0004 (14)
N16	0.0312 (14)	0.0302 (12)	0.0210 (11)	0.0003 (11)	−0.0023 (10)	−0.0028 (10)
C21	0.042 (2)	0.0428 (18)	0.0376 (18)	0.0071 (16)	−0.0056 (16)	−0.0002 (15)
C22	0.057 (3)	0.0360 (18)	0.050 (2)	0.0088 (18)	0.0107 (19)	0.0017 (16)
C23	0.081 (3)	0.0271 (16)	0.0355 (17)	−0.0012 (18)	0.0136 (19)	−0.0033 (14)
C24	0.069 (3)	0.0414 (18)	0.0315 (16)	−0.0119 (19)	−0.0065 (18)	−0.0055 (14)
C25	0.045 (2)	0.0359 (16)	0.0356 (17)	−0.0053 (15)	−0.0066 (15)	−0.0022 (14)
C26	0.0402 (17)	0.0254 (13)	0.0306 (14)	−0.0033 (13)	−0.0011 (14)	0.0029 (11)
C27	0.0308 (16)	0.0355 (16)	0.0300 (15)	−0.0063 (13)	0.0002 (13)	0.0028 (12)
C28	0.0234 (14)	0.0325 (14)	0.0262 (13)	0.0042 (12)	−0.0019 (11)	−0.0024 (11)
C29	0.0252 (14)	0.0369 (15)	0.0285 (14)	0.0042 (13)	−0.0037 (12)	−0.0010 (12)
O30	0.0482 (16)	0.0446 (12)	0.0284 (10)	0.0123 (11)	−0.0047 (10)	0.0039 (9)
N31	0.0313 (14)	0.0341 (12)	0.0213 (11)	0.0058 (11)	−0.0002 (10)	−0.0035 (10)
C32	0.047 (2)	0.0441 (18)	0.0268 (14)	0.0088 (17)	0.0006 (14)	−0.0095 (13)
C33	0.0316 (17)	0.0308 (14)	0.0208 (13)	0.0006 (12)	0.0025 (11)	−0.0026 (11)
C34	0.0381 (19)	0.0408 (18)	0.0381 (17)	−0.0102 (15)	0.0085 (14)	−0.0060 (14)
C35	0.0387 (19)	0.0383 (17)	0.0309 (15)	0.0091 (15)	−0.0001 (13)	0.0021 (13)
N36	0.0264 (13)	0.0330 (13)	0.0200 (11)	−0.0001 (11)	0.0034 (10)	0.0003 (10)
C41	0.0371 (18)	0.0417 (18)	0.0354 (16)	−0.0081 (15)	0.0061 (15)	−0.0039 (14)
C42	0.0363 (18)	0.0447 (19)	0.0366 (17)	−0.0149 (15)	0.0003 (14)	0.0086 (15)
C43	0.050 (2)	0.0312 (16)	0.049 (2)	−0.0070 (16)	−0.0101 (17)	0.0019 (15)
C44	0.052 (2)	0.0383 (19)	0.076 (3)	−0.0032 (19)	0.009 (2)	−0.0229 (18)
C45	0.041 (2)	0.0371 (17)	0.061 (2)	−0.0005 (16)	0.0085 (17)	−0.0091 (16)
C46	0.0326 (18)	0.0288 (13)	0.0277 (13)	−0.0022 (12)	−0.0001 (12)	0.0048 (11)
C47	0.0282 (16)	0.0361 (16)	0.0393 (16)	−0.0051 (13)	0.0070 (14)	−0.0060 (13)
C48	0.0220 (13)	0.0271 (13)	0.0289 (13)	−0.0037 (12)	0.0028 (12)	−0.0002 (11)
C49	0.0245 (16)	0.0347 (15)	0.0267 (13)	−0.0009 (12)	0.0012 (11)	0.0005 (11)
O50	0.0458 (14)	0.0370 (11)	0.0344 (11)	−0.0053 (11)	0.0063 (11)	0.0066 (9)
N51	0.0334 (15)	0.0341 (12)	0.0244 (11)	−0.0047 (11)	0.0033 (11)	0.0016 (10)
C52	0.055 (2)	0.0471 (18)	0.0257 (14)	−0.0105 (19)	0.0005 (16)	−0.0022 (13)
C53	0.0312 (16)	0.0315 (14)	0.0247 (13)	−0.0021 (12)	0.0004 (11)	0.0002 (11)
C54	0.0373 (18)	0.0317 (15)	0.0360 (16)	−0.0089 (14)	−0.0040 (14)	0.0042 (13)
C55	0.0351 (19)	0.0411 (17)	0.0401 (17)	0.0070 (15)	−0.0020 (14)	−0.0070 (14)
N56	0.0263 (13)	0.0301 (13)	0.0240 (11)	−0.0019 (11)	0.0007 (10)	−0.0004 (10)

Geometric parameters (Å, º)

C1—C6	1.379 (5)	C29—O30	1.217 (3)
C1—C2	1.403 (5)	C29—N31	1.343 (4)
C1—H1	0.9500	N31—C32	1.460 (4)
C2—C3	1.381 (7)	N31—C33	1.472 (3)
C2—H2	0.9500	C32—H32A	0.9800
C3—C4	1.367 (6)	C32—H32B	0.9800
C3—H3	0.9500	C32—H32C	0.9800
C4—C5	1.389 (5)	C33—C35	1.511 (4)
C4—H4	0.9500	C33—C34	1.517 (4)
C5—C6	1.393 (5)	C33—N36	1.526 (4)
C5—H5	0.9500	C34—H34A	0.9800
C6—C7	1.510 (4)	C34—H34B	0.9800
C7—C8	1.521 (4)	C34—H34C	0.9800
C7—H7A	0.9900	C35—H35A	0.9800
C7—H7B	0.9900	C35—H35B	0.9800
C8—N16	1.488 (4)	C35—H35C	0.9800
C8—C9	1.527 (4)	N36—H36A	0.874 (17)
C8—H8	1.0000	N36—H36B	0.884 (18)
C9—O10	1.221 (3)	C41—C46	1.375 (4)
C9—N11	1.330 (4)	C41—C42	1.390 (4)
N11—C12	1.455 (4)	C41—H41	0.9500
N11—C13	1.465 (3)	C42—C43	1.363 (5)
C12—H12A	0.9800	C42—H42	0.9500
C12—H12B	0.9800	C43—C44	1.371 (6)
C12—H12C	0.9800	C43—H43	0.9500
C13—C15	1.506 (4)	C44—C45	1.379 (5)
C13—N16	1.518 (4)	C44—H44	0.9500
C13—C14	1.522 (5)	C45—C46	1.384 (4)
C14—H14A	0.9800	C45—H45	0.9500
C14—H14B	0.9800	C46—C47	1.518 (4)
C14—H14C	0.9800	C47—C48	1.515 (4)
C15—H15A	0.9800	C47—H47A	0.9900
C15—H15B	0.9800	C47—H47B	0.9900
C15—H15C	0.9800	C48—N56	1.490 (4)
N16—H16A	0.864 (18)	C48—C49	1.512 (4)
N16—H16B	0.867 (17)	C48—H48	1.0000
C21—C22	1.382 (5)	C49—O50	1.218 (3)
C21—C26	1.387 (5)	C49—N51	1.350 (4)
C21—H21	0.9500	N51—C52	1.448 (4)
C22—C23	1.367 (5)	N51—C53	1.473 (4)
C22—H22	0.9500	C52—H52A	0.9800
C23—C24	1.379 (5)	C52—H52B	0.9800
C23—H23	0.9500	C52—H52C	0.9800
C24—C25	1.390 (5)	C53—N56	1.508 (4)
C24—H24	0.9500	C53—C54	1.510 (4)
C25—C26	1.377 (4)	C53—C55	1.514 (4)
C25—H25	0.9500	C54—H54A	0.9800
C26—C27	1.502 (4)	C54—H54B	0.9800
C27—C28	1.525 (4)	C54—H54C	0.9800
C27—H27A	0.9900	C55—H55A	0.9800
C27—H27B	0.9900	C55—H55B	0.9800
C28—N36	1.500 (4)	C55—H55C	0.9800
C28—C29	1.516 (4)	N56—H56A	0.899 (17)
C28—H28	1.0000	N56—H56B	0.869 (18)
C6—C1—C2	119.8 (4)	C29—N31—C32	123.1 (2)
C6—C1—H1	120.1	C29—N31—C33	114.5 (2)
C2—C1—H1	120.1	C32—N31—C33	120.9 (2)
C3—C2—C1	120.3 (4)	N31—C32—H32A	109.5
C3—C2—H2	119.8	N31—C32—H32B	109.5
C1—C2—H2	119.8	H32A—C32—H32B	109.5
C4—C3—C2	119.9 (4)	N31—C32—H32C	109.5
C4—C3—H3	120.0	H32A—C32—H32C	109.5
C2—C3—H3	120.0	H32B—C32—H32C	109.5
C3—C4—C5	120.3 (4)	N31—C33—C35	112.8 (2)
C3—C4—H4	119.9	N31—C33—C34	111.7 (3)
C5—C4—H4	119.9	C35—C33—C34	112.8 (3)
C4—C5—C6	120.5 (4)	N31—C33—N36	99.4 (2)
C4—C5—H5	119.7	C35—C33—N36	109.5 (2)
C6—C5—H5	119.7	C34—C33—N36	109.8 (2)
C1—C6—C5	119.2 (3)	C33—C34—H34A	109.5
C1—C6—C7	118.6 (3)	C33—C34—H34B	109.5
C5—C6—C7	121.8 (3)	H34A—C34—H34B	109.5
C6—C7—C8	118.9 (3)	C33—C34—H34C	109.5
C6—C7—H7A	107.6	H34A—C34—H34C	109.5
C8—C7—H7A	107.6	H34B—C34—H34C	109.5
C6—C7—H7B	107.6	C33—C35—H35A	109.5
C8—C7—H7B	107.6	C33—C35—H35B	109.5
H7A—C7—H7B	107.0	H35A—C35—H35B	109.5
N16—C8—C7	115.4 (3)	C33—C35—H35C	109.5
N16—C8—C9	101.8 (2)	H35A—C35—H35C	109.5
C7—C8—C9	109.7 (2)	H35B—C35—H35C	109.5
N16—C8—H8	109.9	C28—N36—C33	107.2 (2)
C7—C8—H8	109.9	C28—N36—H36A	111 (2)
C9—C8—H8	109.9	C33—N36—H36A	117 (2)
O10—C9—N11	127.2 (3)	C28—N36—H36B	107 (2)
O10—C9—C8	124.4 (3)	C33—N36—H36B	108 (2)
N11—C9—C8	108.5 (2)	H36A—N36—H36B	106 (3)
C9—N11—C12	122.1 (2)	C46—C41—C42	120.9 (3)
C9—N11—C13	114.4 (2)	C46—C41—H41	119.5
C12—N11—C13	121.7 (2)	C42—C41—H41	119.5
N11—C12—H12A	109.5	C43—C42—C41	120.7 (3)
N11—C12—H12B	109.5	C43—C42—H42	119.7
H12A—C12—H12B	109.5	C41—C42—H42	119.7
N11—C12—H12C	109.5	C42—C43—C44	119.1 (3)
H12A—C12—H12C	109.5	C42—C43—H43	120.4
H12B—C12—H12C	109.5	C44—C43—H43	120.4
N11—C13—C15	112.6 (2)	C43—C44—C45	120.3 (4)
N11—C13—N16	99.6 (2)	C43—C44—H44	119.9
C15—C13—N16	109.2 (3)	C45—C44—H44	119.9
N11—C13—C14	111.0 (3)	C44—C45—C46	121.4 (4)
C15—C13—C14	113.2 (3)	C44—C45—H45	119.3
N16—C13—C14	110.5 (3)	C46—C45—H45	119.3
C13—C14—H14A	109.5	C41—C46—C45	117.6 (3)
C13—C14—H14B	109.5	C41—C46—C47	124.1 (3)
H14A—C14—H14B	109.5	C45—C46—C47	118.2 (3)
C13—C14—H14C	109.5	C48—C47—C46	116.2 (3)
H14A—C14—H14C	109.5	C48—C47—H47A	108.2
H14B—C14—H14C	109.5	C46—C47—H47A	108.2
C13—C15—H15A	109.5	C48—C47—H47B	108.2
C13—C15—H15B	109.5	C46—C47—H47B	108.2
H15A—C15—H15B	109.5	H47A—C47—H47B	107.4
C13—C15—H15C	109.5	N56—C48—C49	101.8 (2)
H15A—C15—H15C	109.5	N56—C48—C47	112.0 (2)
H15B—C15—H15C	109.5	C49—C48—C47	115.6 (3)
C8—N16—C13	107.6 (2)	N56—C48—H48	109.1
C8—N16—H16A	110 (2)	C49—C48—H48	109.1
C13—N16—H16A	106 (2)	C47—C48—H48	109.1
C8—N16—H16B	120 (2)	O50—C49—N51	126.3 (3)
C13—N16—H16B	110 (2)	O50—C49—C48	125.5 (3)
H16A—N16—H16B	101 (3)	N51—C49—C48	108.2 (2)
C22—C21—C26	120.7 (3)	C49—N51—C52	123.1 (3)
C22—C21—H21	119.7	C49—N51—C53	114.4 (2)
C26—C21—H21	119.7	C52—N51—C53	121.8 (2)
C23—C22—C21	120.2 (4)	N51—C52—H52A	109.5
C23—C22—H22	119.9	N51—C52—H52B	109.5
C21—C22—H22	119.9	H52A—C52—H52B	109.5
C22—C23—C24	120.0 (3)	N51—C52—H52C	109.5
C22—C23—H23	120.0	H52A—C52—H52C	109.5
C24—C23—H23	120.0	H52B—C52—H52C	109.5
C23—C24—C25	119.7 (3)	N51—C53—N56	99.5 (2)
C23—C24—H24	120.1	N51—C53—C54	112.9 (2)
C25—C24—H24	120.1	N56—C53—C54	109.9 (2)
C26—C25—C24	120.8 (4)	N51—C53—C55	111.7 (3)
C26—C25—H25	119.6	N56—C53—C55	109.9 (2)
C24—C25—H25	119.6	C54—C53—C55	112.3 (3)
C25—C26—C21	118.5 (3)	C53—C54—H54A	109.5
C25—C26—C27	120.7 (3)	C53—C54—H54B	109.5
C21—C26—C27	120.8 (3)	H54A—C54—H54B	109.5
C26—C27—C28	114.3 (2)	C53—C54—H54C	109.5
C26—C27—H27A	108.7	H54A—C54—H54C	109.5
C28—C27—H27A	108.7	H54B—C54—H54C	109.5
C26—C27—H27B	108.7	C53—C55—H55A	109.5
C28—C27—H27B	108.7	C53—C55—H55B	109.5
H27A—C27—H27B	107.6	H55A—C55—H55B	109.5
N36—C28—C29	101.4 (2)	C53—C55—H55C	109.5
N36—C28—C27	114.5 (2)	H55A—C55—H55C	109.5
C29—C28—C27	114.0 (2)	H55B—C55—H55C	109.5
N36—C28—H28	108.9	C48—N56—C53	108.5 (2)
C29—C28—H28	108.9	C48—N56—H56A	110 (2)
C27—C28—H28	108.9	C53—N56—H56A	117 (2)
O30—C29—N31	126.5 (3)	C48—N56—H56B	104 (2)
O30—C29—C28	125.0 (3)	C53—N56—H56B	110 (2)
N31—C29—C28	108.5 (2)	H56A—N56—H56B	107 (3)

(R4) (R)-5-benzyl-2,2,3-trimethyl-4-oxoimidazolidin-1-ium chloride monohydrate

Crystal data

C13H19N2O^+·Cl^−·H2O	F(000) = 292
Mr = 272.77	Dx = 1.251 Mg m^−3
Monoclinic, P21	Synchrotron radiation, λ = 0.79770 Å
Hall symbol: P 2yb	Cell parameters from 1277 reflections
a = 9.6320 (19) Å	θ = 3.7–25.6°
b = 7.0446 (14) Å	µ = 0.26 mm^−1
c = 11.093 (2) Å	T = 150 K
β = 105.82 (3)°	Block, colourless
V = 724.2 (3) Å^3	0.08 × 0.03 × 0.01 mm
Z = 2

Data collection

Bruker D8 diffractometer	3480 independent reflections
Radiation source: Daresbury SRS, Station 16.2SMX	2485 reflections with I > 2σ(I)
Silicon 111 monochromator	Rint = 0.049
ω rotation with narrow frame scans	θmax = 32.1°, θmin = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −12→12
Tmin = 0.979, Tmax = 1	k = −9→9
6282 measured reflections	l = −13→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.056	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0587P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max < 0.001
3480 reflections	Δρmax = 0.30 e Å^−3
182 parameters	Δρmin = −0.39 e Å^−3
5 restraints	Absolute structure: Flack (1983), 1545 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.15 (9)

Special details

Experimental. A correction to account for beam decay and for absorption was applied using SADABS. Ratio of min/max transmission 0.450.

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1W	0.5949 (3)	0.5880 (4)	0.5927 (2)	0.0357 (6)
Cl1	0.73236 (8)	−0.01536 (10)	0.53347 (8)	0.0319 (2)
C1	0.6492 (3)	0.0160 (4)	0.9371 (3)	0.0275 (8)
H1	0.7328	0.0349	1.0049	0.033*
C2	0.5814 (4)	−0.1589 (5)	0.9230 (3)	0.0316 (8)
H2	0.6168	−0.2581	0.9813	0.038*
C3	0.4610 (4)	−0.1874 (5)	0.8225 (4)	0.0366 (9)
H3	0.4141	−0.3073	0.8111	0.044*
C4	0.4093 (4)	−0.0425 (6)	0.7392 (4)	0.0420 (10)
H4	0.3270	−0.0633	0.6705	0.050*
C5	0.4760 (4)	0.1329 (5)	0.7547 (3)	0.0337 (8)
H5	0.4387	0.2323	0.6970	0.040*
C6	0.5980 (3)	0.1646 (4)	0.8548 (3)	0.0229 (7)
C7	0.6727 (3)	0.3548 (5)	0.8741 (3)	0.0248 (7)
H7A	0.6875	0.3946	0.9622	0.030*
H7B	0.6097	0.4500	0.8199	0.030*
C8	0.8174 (3)	0.3514 (4)	0.8443 (3)	0.0221 (7)
H8	0.8758	0.2427	0.8894	0.027*
C9	0.9036 (3)	0.5347 (4)	0.8786 (3)	0.0222 (7)
O10	0.9149 (2)	0.6252 (3)	0.9741 (2)	0.0328 (6)
N11	0.9619 (3)	0.5769 (4)	0.7829 (2)	0.0222 (6)
C12	1.0484 (4)	0.7448 (5)	0.7802 (4)	0.0319 (8)
H12A	1.0464	0.8278	0.8506	0.048*
H12B	1.0092	0.8129	0.7012	0.048*
H12C	1.1482	0.7069	0.7870	0.048*
C13	0.9429 (3)	0.4239 (4)	0.6898 (3)	0.0207 (7)
C14	1.0675 (4)	0.2802 (5)	0.7256 (3)	0.0286 (8)
H14A	1.1573	0.3418	0.7213	0.043*
H14B	1.0468	0.1728	0.6673	0.043*
H14C	1.0780	0.2344	0.8111	0.043*
C15	0.9194 (3)	0.4956 (5)	0.5573 (3)	0.0264 (7)
H15A	0.8461	0.5958	0.5406	0.040*
H15B	0.8868	0.3908	0.4983	0.040*
H15C	1.0102	0.5466	0.5471	0.040*
N16	0.8062 (3)	0.3367 (4)	0.7071 (2)	0.0217 (6)
H1B	0.500 (3)	0.554 (7)	0.555 (4)	0.091 (19)*
H1A	0.617 (5)	0.711 (4)	0.578 (5)	0.085 (18)*
H16B	0.729 (3)	0.400 (4)	0.667 (3)	0.021 (9)*
H16A	0.795 (4)	0.229 (4)	0.666 (3)	0.041 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1W	0.0283 (14)	0.0269 (14)	0.0457 (16)	0.0008 (11)	0.0000 (12)	0.0063 (11)
Cl1	0.0281 (4)	0.0207 (4)	0.0442 (5)	−0.0007 (4)	0.0055 (3)	−0.0096 (4)
C1	0.0294 (17)	0.022 (2)	0.0291 (17)	−0.0003 (14)	0.0048 (14)	0.0016 (14)
C2	0.0321 (19)	0.0202 (17)	0.042 (2)	0.0029 (15)	0.0095 (16)	0.0036 (16)
C3	0.032 (2)	0.026 (2)	0.055 (3)	−0.0051 (15)	0.0166 (19)	−0.0030 (17)
C4	0.0298 (19)	0.041 (3)	0.046 (2)	−0.0100 (18)	−0.0045 (17)	−0.0030 (19)
C5	0.0286 (19)	0.0303 (19)	0.038 (2)	−0.0013 (15)	0.0020 (16)	0.0058 (16)
C6	0.0236 (17)	0.0196 (16)	0.0265 (17)	−0.0011 (13)	0.0084 (14)	−0.0012 (13)
C7	0.0270 (17)	0.0197 (16)	0.0289 (17)	0.0014 (13)	0.0093 (14)	0.0010 (14)
C8	0.0258 (17)	0.0150 (14)	0.0257 (17)	0.0025 (13)	0.0074 (14)	0.0035 (13)
C9	0.0221 (16)	0.0168 (16)	0.0254 (16)	0.0023 (11)	0.0027 (13)	0.0011 (12)
O10	0.0336 (14)	0.0347 (14)	0.0283 (13)	−0.0061 (11)	0.0055 (11)	−0.0105 (11)
N11	0.0259 (14)	0.0141 (12)	0.0242 (14)	−0.0034 (11)	0.0029 (11)	0.0004 (10)
C12	0.031 (2)	0.0214 (17)	0.042 (2)	−0.0088 (14)	0.0071 (17)	0.0043 (15)
C13	0.0216 (16)	0.0161 (15)	0.0239 (17)	−0.0007 (11)	0.0051 (13)	0.0002 (12)
C14	0.0279 (18)	0.0227 (17)	0.036 (2)	0.0042 (14)	0.0101 (16)	0.0061 (14)
C15	0.0307 (16)	0.0235 (16)	0.0255 (16)	0.0023 (17)	0.0083 (13)	0.0038 (15)
N16	0.0228 (14)	0.0180 (13)	0.0228 (15)	−0.0017 (11)	0.0040 (12)	−0.0033 (11)

Geometric parameters (Å, º)

O1W—H1B	0.93 (2)	C8—H8	1.0000
O1W—H1A	0.92 (2)	C9—O10	1.215 (4)
C1—C2	1.383 (5)	C9—N11	1.362 (4)
C1—C6	1.388 (4)	N11—C12	1.452 (4)
C1—H1	0.9500	N11—C13	1.470 (4)
C2—C3	1.387 (5)	C12—H12A	0.9800
C2—H2	0.9500	C12—H12B	0.9800
C3—C4	1.375 (5)	C12—H12C	0.9800
C3—H3	0.9500	C13—C15	1.512 (4)
C4—C5	1.382 (5)	C13—N16	1.512 (4)
C4—H4	0.9500	C13—C14	1.538 (4)
C5—C6	1.398 (5)	C14—H14A	0.9800
C5—H5	0.9500	C14—H14B	0.9800
C6—C7	1.508 (5)	C14—H14C	0.9800
C7—C8	1.517 (4)	C15—H15A	0.9800
C7—H7A	0.9900	C15—H15B	0.9800
C7—H7B	0.9900	C15—H15C	0.9800
C8—N16	1.500 (4)	N16—H16B	0.877 (18)
C8—C9	1.526 (4)	N16—H16A	0.877 (19)
H1B—O1W—H1A	114 (5)	C9—N11—C12	123.7 (3)
C2—C1—C6	121.7 (3)	C9—N11—C13	112.9 (2)
C2—C1—H1	119.1	C12—N11—C13	123.0 (3)
C6—C1—H1	119.1	N11—C12—H12A	109.5
C1—C2—C3	119.0 (3)	N11—C12—H12B	109.5
C1—C2—H2	120.5	H12A—C12—H12B	109.5
C3—C2—H2	120.5	N11—C12—H12C	109.5
C4—C3—C2	120.2 (3)	H12A—C12—H12C	109.5
C4—C3—H3	119.9	H12B—C12—H12C	109.5
C2—C3—H3	119.9	N11—C13—C15	113.3 (2)
C3—C4—C5	120.6 (3)	N11—C13—N16	98.9 (2)
C3—C4—H4	119.7	C15—C13—N16	110.8 (2)
C5—C4—H4	119.7	N11—C13—C14	111.2 (3)
C4—C5—C6	120.2 (3)	C15—C13—C14	111.7 (3)
C4—C5—H5	119.9	N16—C13—C14	110.2 (3)
C6—C5—H5	119.9	C13—C14—H14A	109.5
C1—C6—C5	118.2 (3)	C13—C14—H14B	109.5
C1—C6—C7	120.5 (3)	H14A—C14—H14B	109.5
C5—C6—C7	121.3 (3)	C13—C14—H14C	109.5
C6—C7—C8	112.7 (3)	H14A—C14—H14C	109.5
C6—C7—H7A	109.0	H14B—C14—H14C	109.5
C8—C7—H7A	109.0	C13—C15—H15A	109.5
C6—C7—H7B	109.0	C13—C15—H15B	109.5
C8—C7—H7B	109.0	H15A—C15—H15B	109.5
H7A—C7—H7B	107.8	C13—C15—H15C	109.5
N16—C8—C7	113.9 (3)	H15A—C15—H15C	109.5
N16—C8—C9	101.3 (2)	H15B—C15—H15C	109.5
C7—C8—C9	113.7 (3)	C8—N16—C13	106.1 (2)
N16—C8—H8	109.2	C8—N16—H16B	108 (2)
C7—C8—H8	109.2	C13—N16—H16B	112 (2)
C9—C8—H8	109.2	C8—N16—H16A	123 (3)
O10—C9—N11	127.3 (3)	C13—N16—H16A	106 (2)
O10—C9—C8	125.1 (3)	H16B—N16—H16A	102 (3)
N11—C9—C8	107.6 (3)

(S4) (S)-5-benzyl-2,2,3-trimethyl-4-oxoimidazolidin-1-ium chloride monohydrate

Crystal data

C13H19N2O^+·Cl^−·H2O	F(000) = 292
Mr = 272.77	Dx = 1.249 Mg m^−3
Monoclinic, P21	Synchrotron radiation, λ = 0.79770 Å
Hall symbol: P 2yb	Cell parameters from 914 reflections
a = 9.6425 (14) Å	θ = 3.7–24.1°
b = 7.0517 (10) Å	µ = 0.26 mm^−1
c = 11.0895 (16) Å	T = 150 K
β = 105.796 (2)°	Square plate, colourless
V = 725.57 (18) Å^3	0.04 × 0.04 × 0.01 mm
Z = 2

Data collection

Bruker D8 diffractometer	3330 independent reflections
Radiation source: Daresbury SRS, Station 16.2SMX	2438 reflections with I > 2σ(I)
Silicon 111 monochromator	Rint = 0.052
ω rotation with narrow frame scans	θmax = 32.4°, θmin = 3.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −12→12
Tmin = 0.987, Tmax = 0.99	k = −9→9
6377 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.122	w = 1/[σ^2(Fo^2) + (0.0529P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max < 0.001
3330 reflections	Δρmax = 0.27 e Å^−3
181 parameters	Δρmin = −0.38 e Å^−3
5 restraints	Absolute structure: Flack (1983), 1339 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (9)

Special details

Experimental. A correction to account for beam decay and for absorption was applied using SADABS. Ratio of min/max transmission 0.56.

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1W	0.4053 (3)	0.4119 (4)	0.4073 (3)	0.0331 (6)
H1B	0.499 (3)	0.441 (7)	0.453 (4)	0.089 (14)*
H1A	0.386 (6)	0.289 (4)	0.423 (5)	0.089 (14)*
Cl1	0.26752 (8)	1.01537 (11)	0.46663 (8)	0.0286 (2)
C1	0.3516 (4)	0.9829 (5)	0.0632 (3)	0.0251 (8)
H1	0.2683	0.9634	−0.0048	0.030*
C2	0.4190 (4)	1.1592 (5)	0.0771 (3)	0.0294 (8)
H2	0.3828	1.2587	0.0193	0.035*
C3	0.5404 (4)	1.1868 (6)	0.1773 (4)	0.0347 (9)
H3	0.5883	1.3058	0.1880	0.042*
C4	0.5914 (4)	1.0420 (6)	0.2610 (4)	0.0388 (10)
H4	0.6730	1.0627	0.3303	0.047*
C5	0.5247 (4)	0.8670 (5)	0.2448 (3)	0.0292 (8)
H5	0.5626	0.7673	0.3020	0.035*
C6	0.4024 (4)	0.8347 (5)	0.1457 (3)	0.0199 (7)
C7	0.3281 (3)	0.6452 (5)	0.1261 (3)	0.0216 (7)
H7A	0.3906	0.5500	0.1806	0.026*
H7B	0.3141	0.6053	0.0380	0.026*
C8	0.1818 (3)	0.6490 (5)	0.1551 (3)	0.0178 (7)
H8	0.1231	0.7572	0.1098	0.021*
C9	0.0976 (3)	0.4657 (4)	0.1218 (3)	0.0186 (7)
O10	0.0850 (2)	0.3747 (4)	0.0258 (2)	0.0288 (6)
N11	0.0383 (3)	0.4234 (4)	0.2169 (2)	0.0195 (6)
C12	−0.0486 (4)	0.2561 (5)	0.2200 (3)	0.0284 (8)
H12A	−0.0527	0.1774	0.1462	0.043*
H12B	−0.1463	0.2949	0.2195	0.043*
H12C	−0.0053	0.1832	0.2962	0.043*
C13	0.0567 (3)	0.5769 (4)	0.3105 (3)	0.0180 (7)
C14	−0.0673 (4)	0.7197 (5)	0.2744 (3)	0.0235 (7)
H14A	−0.1569	0.6584	0.2791	0.035*
H14B	−0.0778	0.7646	0.1888	0.035*
H14C	−0.0465	0.8275	0.3323	0.035*
C15	0.0808 (3)	0.5036 (6)	0.4428 (3)	0.0241 (7)
H15A	0.1505	0.3992	0.4573	0.036*
H15B	−0.0107	0.4579	0.4543	0.036*
H15C	0.1182	0.6061	0.5024	0.036*
N16	0.1943 (3)	0.6638 (4)	0.2933 (2)	0.0179 (6)
H16B	0.265 (3)	0.585 (5)	0.330 (4)	0.056 (14)*
H16A	0.206 (4)	0.777 (3)	0.327 (4)	0.046 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1W	0.0236 (13)	0.0284 (15)	0.0403 (16)	0.0039 (12)	−0.0032 (11)	0.0087 (12)
Cl1	0.0241 (4)	0.0222 (4)	0.0367 (5)	−0.0002 (4)	0.0034 (3)	−0.0085 (4)
C1	0.0295 (17)	0.023 (2)	0.0203 (17)	−0.0003 (15)	0.0031 (13)	0.0020 (14)
C2	0.032 (2)	0.0206 (18)	0.037 (2)	−0.0014 (16)	0.0108 (17)	0.0004 (16)
C3	0.029 (2)	0.030 (2)	0.048 (2)	−0.0045 (17)	0.0160 (19)	−0.0012 (19)
C4	0.0258 (19)	0.042 (3)	0.040 (2)	−0.0091 (19)	−0.0063 (16)	0.002 (2)
C5	0.0249 (19)	0.032 (2)	0.0273 (19)	0.0010 (16)	0.0004 (15)	0.0080 (16)
C6	0.0211 (17)	0.0214 (17)	0.0177 (16)	0.0041 (14)	0.0061 (13)	0.0014 (13)
C7	0.0215 (17)	0.0229 (18)	0.0205 (16)	0.0001 (14)	0.0060 (13)	0.0015 (14)
C8	0.0212 (16)	0.0179 (16)	0.0143 (15)	−0.0046 (14)	0.0047 (12)	−0.0005 (13)
C9	0.0186 (16)	0.0158 (17)	0.0189 (16)	0.0002 (12)	0.0009 (13)	0.0005 (12)
O10	0.0314 (14)	0.0339 (14)	0.0191 (12)	−0.0060 (12)	0.0033 (10)	−0.0078 (11)
N11	0.0212 (14)	0.0174 (13)	0.0187 (14)	−0.0060 (12)	0.0035 (11)	−0.0006 (11)
C12	0.029 (2)	0.0274 (19)	0.027 (2)	−0.0064 (16)	0.0051 (16)	0.0018 (15)
C13	0.0164 (16)	0.0158 (15)	0.0207 (17)	0.0013 (12)	0.0034 (13)	0.0010 (12)
C14	0.0229 (18)	0.0238 (18)	0.0228 (18)	0.0050 (15)	0.0044 (14)	0.0017 (14)
C15	0.0269 (16)	0.0253 (17)	0.0196 (16)	−0.0021 (19)	0.0057 (12)	0.0011 (16)
N16	0.0197 (14)	0.0148 (14)	0.0173 (14)	0.0007 (12)	0.0021 (11)	−0.0019 (12)

Geometric parameters (Å, º)

O1W—H1B	0.93 (2)	C8—H8	1.0000
O1W—H1A	0.912 (19)	C9—O10	1.220 (4)
C1—C6	1.388 (4)	C9—N11	1.362 (4)
C1—C2	1.392 (5)	N11—C12	1.453 (4)
C1—H1	0.9500	N11—C13	1.476 (4)
C2—C3	1.391 (5)	C12—H12A	0.9800
C2—H2	0.9500	C12—H12B	0.9800
C3—C4	1.377 (6)	C12—H12C	0.9800
C3—H3	0.9500	C13—C15	1.512 (4)
C4—C5	1.381 (5)	C13—N16	1.520 (4)
C4—H4	0.9500	C13—C14	1.531 (4)
C5—C6	1.395 (5)	C14—H14A	0.9800
C5—H5	0.9500	C14—H14B	0.9800
C6—C7	1.504 (5)	C14—H14C	0.9800
C7—C8	1.530 (4)	C15—H15A	0.9800
C7—H7A	0.9900	C15—H15B	0.9800
C7—H7B	0.9900	C15—H15C	0.9800
C8—N16	1.508 (4)	N16—H16B	0.89 (2)
C8—C9	1.517 (4)	N16—H16A	0.874 (19)
H1B—O1W—H1A	109 (5)	C9—N11—C12	124.2 (3)
C6—C1—C2	122.0 (3)	C9—N11—C13	112.9 (2)
C6—C1—H1	119.0	C12—N11—C13	122.6 (3)
C2—C1—H1	119.0	N11—C12—H12A	109.5
C3—C2—C1	118.6 (3)	N11—C12—H12B	109.5
C3—C2—H2	120.7	H12A—C12—H12B	109.5
C1—C2—H2	120.7	N11—C12—H12C	109.5
C4—C3—C2	120.2 (4)	H12A—C12—H12C	109.5
C4—C3—H3	119.9	H12B—C12—H12C	109.5
C2—C3—H3	119.9	N11—C13—C15	112.9 (3)
C3—C4—C5	120.5 (3)	N11—C13—N16	98.6 (2)
C3—C4—H4	119.8	C15—C13—N16	110.6 (2)
C5—C4—H4	119.8	N11—C13—C14	111.2 (3)
C4—C5—C6	120.8 (3)	C15—C13—C14	112.4 (3)
C4—C5—H5	119.6	N16—C13—C14	110.4 (3)
C6—C5—H5	119.6	C13—C14—H14A	109.5
C1—C6—C5	117.9 (3)	C13—C14—H14B	109.5
C1—C6—C7	120.4 (3)	H14A—C14—H14B	109.5
C5—C6—C7	121.8 (3)	C13—C14—H14C	109.5
C6—C7—C8	112.6 (3)	H14A—C14—H14C	109.5
C6—C7—H7A	109.1	H14B—C14—H14C	109.5
C8—C7—H7A	109.1	C13—C15—H15A	109.5
C6—C7—H7B	109.1	C13—C15—H15B	109.5
C8—C7—H7B	109.1	H15A—C15—H15B	109.5
H7A—C7—H7B	107.8	C13—C15—H15C	109.5
N16—C8—C9	101.3 (2)	H15A—C15—H15C	109.5
N16—C8—C7	113.1 (2)	H15B—C15—H15C	109.5
C9—C8—C7	113.4 (3)	C8—N16—C13	105.6 (2)
N16—C8—H8	109.6	C8—N16—H16B	106 (3)
C9—C8—H8	109.6	C13—N16—H16B	106 (3)
C7—C8—H8	109.6	C8—N16—H16A	117 (3)
O10—C9—N11	126.7 (3)	C13—N16—H16A	109 (3)
O10—C9—C8	125.4 (3)	H16B—N16—H16A	112 (4)
N11—C9—C8	107.9 (3)