A hydrogen-bonded three-component complex: bis­(di­cyclo­hexyl­ammonium) 2,4-di­chloro­phenolate 2,4,6-tri­chloro­phenolate 2,4-di­chloro­phenol

The title complex, 2C₁₂H₂₄N⁺·C₆H₃Cl₂O⁻·C₆H₂Cl₃O⁻·C₆H₄Cl₂O, consists of three different achiral components, dicyclohexylammonium cations, 2,4,6-trichlorophenolate anions and H-atom-bridged 2,4-dichlorophenolate/2,4-dichlorophenol units, held together by O—H...N and O—H...O hydrogen bonds to form a chiral hydrogen-bonded ring. A helical cylinder is established by the packing of these rings along a crystallographic 4₁ screw axes. Helical cylinders may be generated from each other by translation, resulting in the formation of the chiral crystal. Neighbouring parallel helical cylinders are associated by van der Waals inter­actions only.

S1. Introduction

Most achiral organic compounds tend to crystalize in achiral space groups. However, a few may crystalize in chiral space groups, which is often discovered by accident and is considered as a rare phenomenon (Koshima et al., 1996, 1997; Matsuura & Koshima, 2005). In the literature, there have been a few reports of chiral cocrystals containing di­cyclo­hexyl­ammonium as one of the achiral components (Golobic et al., 1999; Melendez et al. 1996; Trivedi et al., 2004, 2005; Ballabh et al. 2005; Bi et al. 2002).

S2. Experimental

S2.1. Synthesis and crystallization

2,4-Di­chloro­phenol (3.3 g, 200 mmol), di­cyclo­hexyl­amine (3.6 g, 200 mmol) and 2,4,6-tri­chloro­phenol (2.0 g, 100 mmol) were mixed and dissolved in sufficient anhydrous ethanol (20 ml) by heating to 323 K to give a clear solution. Single crystals of (I) were formed by slow evaporation of the solvent after one week at 293 K. IR (KBr): 3040.1, 2941.5, 2862.4, 2547.6, 2461.8, 1631.9, 1607.3, 1447.7, 1291.2, 1050.4, 816.7, 594.0, 554.7, 488.4, 446.5 cm^-1. ¹H NMR (500 MHz, CD₃Cl): δ 1.09–1.99 (m, 20H), 2.85 (m, 2H), 5.721 (s, 2.5H), 6.869 (d, 1H), 7.064 (dd, 1H), 7.184 (s, 1H), 7.307 (d, 1H).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The atoms of H1C, H1D and H1 were deduced from an difference electron-density map and refined freely. The other H atoms were placed in calculated positions and allowed to ride on their parent atoms at C—H distances of 0.93 Å for phenyl, 0.97 Å for methyl­ene and 0.98 Å for methine, with U_iso(H) = 1.2U_eq of the parent atoms.

S3. Results and discussion

The title complex, (I), was synthesized from three achiral compounds, 2,4-di­chloro­phenol, di­hexyl­cyclo­amine and 2,4,6-tri­chloro­phenol (Scheme 1), and it crystallizes in the chiral space group P4₁22 (Table 1 and Fig. 1). In the asymmetric unit of (I), there are one each of the di­cyclo­hexyl­ammonium and 2,4-di­chloro­phenolate ions, and a half of a 2,4,6-tri­chloro­phenolate ion (Fig. 1). The title complex is built by a combination of two asymmetric units, which may be generated from each other by the C2-symmetry operation taking the centre line (O2—C22—C19—Cl3) of the 2,4,6-tri­chloro­phenolate ion as the axis. This centre line is exactly parallel to the (110) direction. The C21—C22 bond length (Table 2) is much longer than normal aromatic C—C bonds, due to static electronic repulsion between the Cl3 and O2 atoms. This situation is different from that of neutral 2,4,6-tri­chloro­phenol in the solid state (González Martínez & Bernès, 2007), but is similar to those of the 2,3,4,5,6-penta­chloro­phenolate anion (Majerz et al. 1998; Sawka-Dobrowolska et al. 1995). In (I), five molecules of the three different components are associated by hydrogen bonds. Further, the di­cyclo­hexyl­ammonium ion shows a conformation with pseudo-C2 symmetry, taking the mid-line of the C1—N1—C7 isosceles triangle as the axis.

In the title complex, two C2-symmetrically related 2,4-di­chloro­phenolate ions are held together by an extremely short symmetrical hydrogen bond O1···H1···O1(-y + 1, -x+1, -z+1/4) (Fig. 1 and Table 3), with atom H1 located centrally on the C2 symmetry axis. The aromatic ring planes of 2,4-di­chloro­phenolate and its symmetry equivalent at (-y+1, -x+1, -z+1/4) inter­sect on the O1—O1(-y+1, -x+1, -z+1/4) line, with a dihedral angle of 111.5 (6)°. The hydrogen-bonded pair of 2,4-di­chloro­phenolate anions are further combined with two di­cyclo­hexyl­ammonium and one 2,4,6-tri­chloro­phenolate ion by N1—H1C···O1 and N1—H1D···O1 hydrogen bonds (Fig. 1 and Table 3) to form a chiral hydrogen-bonded ring (Fig. 1), which may be described with the graph-set R₅³(10) (Etter, 1990; Grell et al., 1999), where one 2,4-di­chloro­phenolate ion is acting as a hydrogen-bond donor and the other as an acceptor. The hydrogen-bond donors and acceptors, O1, O1(-y+1, -x+1, -z +1/4), O2, N1, and N1(-y+1, -x+1, -z+1/4), are arranged in a roughly flat penta­gonal geometry. Viewed along the c axis (Fig. 1), the title complex looks like a propeller.

Previously, a survey showed that hydrogen-bonded rings are rarely observed in crystals of chiral molecules (Eppel & Bernstein, 2008); but they are frequently observed in crystals of achiral molecules, bearing an inversion centre. Unfortunately, cases of chiral crystals built of achiral molecules hadn't been distinguished from achiral crystals built of achiral molecules in in the survey. Taking cocrystals containing di­cyclo­hexyl­ammino ions as instances (Golobic et al., 1999; Melendez et al. 1996; Trivedi et al., 2004, 2005; Ballabh et al. 2005; Bi et al. 2002), one might add that hydrogen-bonded rings are rarely observed in chiral crystals, regardless of the chirality of the components involved. And, it is found that the title complex is an exceptional case.

The hydrogen-bonded rings are aligned one after another along the c axis, and successive rings may be symmetry generated from each other by twisting by 90° in the (110) plane and by translating 1/4 the length of the c axis (Fig. 2). Therefore, a helical cylinder of rings is established, parallel to the c axis. Neighbouring helical cylinders are inter­related by translation, resulting in the formation of the chiral crystal. The formation of the chiral cocrystal may be ascribed to the steric hindrance of the bulky di­cyclo­hexyl group, inferred from the mechanism suggested previously (Ueki & Soloshonok, 2009; Lemmerer et al., 2011). There is no strong inter­molecular contact between the successive rings. Neighbouring helical cylinders are associated with each other by van der Waals inter­actions. Due to the steric hindrance, there are no π–π or C—H···π contacts. However, two short Cl···Cl contacts are observed, with separations close to double the van der Waals radius of the Cl atom (Pauling & Pauling, 1975), namely Cl1···Cl4(-y+2, -x+1, -z+1/4) [3.742 (5) Å] and Cl2···Cl2(x, -y, -z+1/2) [3.844 (5) Å].

Related literature

For related literature, see: Ballabh et al. (2005); Bi et al. (2002); Eppel & Bernstein (2008); Etter (1990); Golobic et al. (1999); Grell et al. (1999); Koshima et al. (1996, 1997); Lemmerer (2011); Majerz et al. (1998); González Martínez & Bernès (2007); Matsuura & Koshima (2005); Sawka-Dobrowolska, Grech, Brzezinski, Malarski & Sobczyk (1995); Trivedi et al. (2004, 2005); Ueki & Soloshonok (2009).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The two cation plus three anion unit of (I) with atom labels, showing 40% probability displacement ellipsoids. The unlabeled parts are the C2-symmetric image, generated by the symmetry operation (-y + 1, -x + 1, -z + 1/4). Hydrogen bonding is illustrated as dashed lines, with hydrogen atoms except H1C, H1D and H1 and their symmetry equivalents omitted for clarity.

Fig. 2. The packing of the hydrogen-bonded rings running along the c axis, viewed parallel to b. Hydrogen bonding is shown by dashed lines, with hydrogen atoms not involved in hydrogen bonding omitted for clarity.

Bis(dicyclohexylammonium) 2,4-dichlorophenolate 2,4,6-trichlorophenolate 2,4-dichlorophenol

Crystal data

2C12H24N^+·C6H3Cl2O^−·C6H2Cl3O^−·C6H4Cl2O	Dx = 1.310 Mg m^−3
Mr = 886.05	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4122	Cell parameters from 2879 reflections
a = 10.604 (1) Å	θ = 2.1–23.1°
c = 39.960 (9) Å	µ = 0.48 mm^−1
V = 4493.3 (12) Å^3	T = 293 K
Z = 4	Prism, colorless
F(000) = 1864	0.34 × 0.32 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4422 independent reflections
Radiation source: fine-focus sealed tube	3563 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
φ and ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→13
Tmin = 0.893, Tmax = 0.918	k = −9→13
25411 measured reflections	l = −44→49

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) = 0.146	w = 1/[σ^2(Fo^2) + (0.0916P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max < 0.001
4422 reflections	Δρmax = 0.33 e Å^−3
245 parameters	Δρmin = −0.32 e Å^−3
0 restraints	Absolute structure: Flack & Bernardinelli (1999), 1763 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (9)

Special details

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

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 > 2sigma(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
C1	0.6792 (4)	0.5410 (4)	0.06619 (8)	0.0659 (10)
H1A	0.5885	0.5323	0.0682	0.079*
H1B	0.7173	0.4596	0.0708	0.079*
C2	0.7132 (4)	0.5833 (5)	0.03085 (9)	0.0770 (12)
H2A	0.6879	0.5186	0.0150	0.092*
H2B	0.6670	0.6597	0.0255	0.092*
C3	0.8515 (4)	0.6076 (5)	0.02726 (10)	0.0828 (13)
H3A	0.8685	0.6382	0.0048	0.099*
H3B	0.8970	0.5290	0.0302	0.099*
C4	0.8993 (5)	0.7035 (5)	0.05254 (9)	0.0831 (13)
H4A	0.8608	0.7849	0.0482	0.100*
H4B	0.9899	0.7126	0.0504	0.100*
C5	0.8664 (4)	0.6600 (4)	0.08825 (9)	0.0662 (10)
H5A	0.9116	0.5828	0.0934	0.079*
H5B	0.8921	0.7239	0.1042	0.079*
C6	0.7266 (3)	0.6375 (3)	0.09116 (8)	0.0514 (8)
H6	0.6838	0.7174	0.0864	0.062*
C7	0.7204 (3)	0.6820 (3)	0.15414 (7)	0.0463 (7)
H7	0.8117	0.6963	0.1545	0.056*
C8	0.6818 (4)	0.6157 (4)	0.18605 (8)	0.0560 (8)
H8A	0.7275	0.5368	0.1882	0.067*
H8B	0.5923	0.5968	0.1854	0.067*
C9	0.7108 (5)	0.7006 (5)	0.21589 (10)	0.0770 (12)
H9A	0.6829	0.6593	0.2362	0.092*
H9B	0.8013	0.7126	0.2175	0.092*
C10	0.6497 (5)	0.8230 (5)	0.21323 (11)	0.0921 (15)
H10A	0.6760	0.8754	0.2318	0.110*
H10B	0.5591	0.8118	0.2147	0.110*
C11	0.6814 (5)	0.8900 (4)	0.18044 (10)	0.0789 (12)
H11A	0.6326	0.9671	0.1789	0.095*
H11B	0.7700	0.9126	0.1804	0.095*
C12	0.6535 (4)	0.8080 (3)	0.15031 (9)	0.0622 (9)
H12A	0.6822	0.8498	0.1301	0.075*
H12B	0.5633	0.7945	0.1484	0.075*
C13	0.85606 (19)	0.31031 (18)	0.16520 (4)	0.0455 (7)
C14	0.9499 (2)	0.38293 (17)	0.18001 (6)	0.0526 (8)
C15	1.0078 (2)	0.3418 (2)	0.20925 (6)	0.0667 (11)
H15	1.0705	0.3904	0.2191	0.080*
C16	0.9719 (2)	0.2281 (2)	0.22368 (5)	0.0701 (11)
C17	0.8781 (2)	0.1555 (2)	0.20887 (5)	0.0691 (11)
H17	0.8541	0.0794	0.2185	0.083*
C18	0.8202 (2)	0.19657 (19)	0.17964 (5)	0.0621 (9)
H18	0.7574	0.1480	0.1697	0.074*
C19	0.1591 (4)	0.8409 (4)	0.1250	0.0694 (15)
C20	0.2148 (4)	0.8104 (4)	0.09596 (10)	0.0641 (10)
H20	0.1924	0.8515	0.0763	0.077*
C21	0.3062 (4)	0.7166 (3)	0.09563 (8)	0.0559 (9)
C22	0.3481 (3)	0.6519 (3)	0.1250	0.0465 (10)
Cl1	1.00087 (10)	0.51891 (9)	0.16186 (3)	0.0741 (3)
Cl2	1.04267 (9)	0.17755 (10)	0.25968 (2)	0.0683 (3)
Cl3	0.04269 (8)	0.95731 (8)	0.1250	0.0675 (4)
Cl4	0.37592 (10)	0.68113 (10)	0.05872 (2)	0.0688 (3)
N1	0.6888 (3)	0.5968 (3)	0.12552 (7)	0.0453 (6)
O1	0.7965 (2)	0.3526 (2)	0.13720 (5)	0.0470 (5)
O2	0.4336 (2)	0.5664 (2)	0.1250	0.0505 (7)
H1C	0.606 (3)	0.591 (3)	0.1252 (8)	0.046 (9)*
H1D	0.716 (4)	0.519 (4)	0.1312 (9)	0.064 (11)*
H1	0.725 (3)	0.275 (3)	0.1250	0.057 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.069 (2)	0.075 (3)	0.0541 (19)	−0.021 (2)	0.0072 (18)	−0.0144 (19)
C2	0.083 (3)	0.100 (3)	0.048 (2)	−0.005 (2)	0.005 (2)	−0.008 (2)
C3	0.074 (3)	0.117 (4)	0.057 (2)	0.007 (3)	0.014 (2)	−0.001 (2)
C4	0.080 (3)	0.108 (4)	0.062 (2)	−0.028 (3)	0.015 (2)	0.014 (2)
C5	0.055 (2)	0.083 (3)	0.0604 (19)	−0.0226 (19)	0.0091 (18)	−0.0037 (19)
C6	0.060 (2)	0.0433 (18)	0.0512 (17)	−0.0037 (16)	0.0052 (15)	−0.0025 (15)
C7	0.0425 (17)	0.0433 (17)	0.0533 (17)	−0.0083 (14)	0.0029 (13)	−0.0148 (14)
C8	0.0506 (19)	0.057 (2)	0.0609 (19)	−0.0011 (16)	0.0043 (16)	−0.0020 (17)
C9	0.079 (3)	0.089 (3)	0.063 (2)	−0.012 (2)	0.006 (2)	−0.015 (2)
C10	0.103 (4)	0.092 (3)	0.082 (3)	−0.009 (3)	0.019 (3)	−0.038 (3)
C11	0.088 (3)	0.053 (2)	0.095 (3)	−0.011 (2)	0.020 (3)	−0.031 (2)
C12	0.064 (2)	0.0452 (19)	0.077 (2)	−0.0055 (17)	0.0083 (19)	−0.0032 (18)
C13	0.0455 (17)	0.0385 (15)	0.0525 (17)	−0.0034 (14)	−0.0028 (14)	−0.0081 (14)
C14	0.0394 (16)	0.056 (2)	0.0624 (19)	−0.0027 (15)	−0.0077 (15)	−0.0131 (17)
C15	0.0485 (19)	0.092 (3)	0.060 (2)	0.001 (2)	−0.0134 (17)	−0.027 (2)
C16	0.056 (2)	0.103 (3)	0.052 (2)	0.000 (2)	−0.0150 (18)	−0.003 (2)
C17	0.068 (2)	0.083 (3)	0.056 (2)	−0.009 (2)	−0.0137 (18)	0.0164 (19)
C18	0.062 (2)	0.058 (2)	0.067 (2)	−0.0139 (18)	−0.0178 (18)	0.0032 (18)
C19	0.0527 (19)	0.0527 (19)	0.103 (5)	−0.009 (2)	0.001 (2)	0.001 (2)
C20	0.060 (2)	0.053 (2)	0.079 (2)	−0.0129 (18)	−0.0163 (19)	0.0084 (19)
C21	0.060 (2)	0.052 (2)	0.0558 (19)	−0.0215 (17)	0.0007 (16)	0.0025 (16)
C22	0.0394 (15)	0.0394 (15)	0.061 (3)	−0.0107 (19)	−0.0040 (13)	−0.0040 (13)
Cl1	0.0578 (5)	0.0603 (6)	0.1041 (8)	−0.0168 (4)	−0.0085 (5)	−0.0097 (5)
Cl2	0.0635 (5)	0.0773 (6)	0.0640 (5)	0.0151 (5)	−0.0168 (4)	0.0172 (5)
Cl3	0.0645 (5)	0.0645 (5)	0.0737 (8)	0.0187 (6)	−0.0077 (5)	−0.0077 (5)
Cl4	0.0734 (7)	0.0708 (6)	0.0621 (5)	0.0063 (5)	0.0028 (5)	0.0035 (5)
N1	0.0489 (17)	0.0412 (15)	0.0458 (14)	−0.0027 (12)	0.0050 (13)	−0.0005 (11)
O1	0.0545 (13)	0.0413 (12)	0.0453 (11)	−0.0058 (10)	−0.0092 (10)	−0.0058 (9)
O2	0.0485 (11)	0.0485 (11)	0.0545 (18)	−0.0073 (15)	−0.0023 (10)	−0.0023 (10)

Geometric parameters (Å, º)

C1—C6	1.515 (5)	C10—H10B	0.9700
C1—C2	1.525 (5)	C11—C12	1.514 (5)
C1—H1A	0.9700	C11—H11A	0.9700
C1—H1B	0.9700	C11—H11B	0.9700
C2—C3	1.497 (6)	C12—H12A	0.9700
C2—H2A	0.9700	C12—H12B	0.9700
C2—H2B	0.9700	C13—O1	1.361 (2)
C3—C4	1.521 (6)	C13—C14	1.3900
C3—H3A	0.9700	C13—C18	1.3900
C3—H3B	0.9700	C14—C15	1.3900
C4—C5	1.540 (5)	C14—Cl1	1.702 (2)
C4—H4A	0.9700	C15—C16	1.3900
C4—H4B	0.9700	C15—H15	0.9300
C5—C6	1.506 (5)	C16—C17	1.3900
C5—H5A	0.9700	C16—Cl2	1.7087 (17)
C5—H5B	0.9700	C17—C18	1.3900
C6—N1	1.494 (4)	C17—H17	0.9300
C6—H6	0.9800	C18—H18	0.9300
C7—N1	1.495 (4)	C19—C20^i	1.342 (5)
C7—C8	1.513 (5)	C19—C20	1.342 (5)
C7—C12	1.520 (5)	C19—Cl3	1.745 (6)
C7—H7	0.9800	C20—C21	1.389 (6)
C8—C9	1.525 (5)	C20—H20	0.9300
C8—H8A	0.9700	C21—C22	1.430 (4)
C8—H8B	0.9700	C21—Cl4	1.692 (4)
C9—C10	1.455 (7)	C22—O2	1.282 (5)
C9—H9A	0.9700	C22—C21^i	1.430 (4)
C9—H9B	0.9700	N1—H1C	0.88 (4)
C10—C11	1.528 (6)	N1—H1D	0.90 (4)
C10—H10A	0.9700	O1—H1	1.22 (3)
C6—C1—C2	109.4 (3)	C9—C10—H10A	109.1
C6—C1—H1A	109.8	C11—C10—H10A	109.1
C2—C1—H1A	109.8	C9—C10—H10B	109.1
C6—C1—H1B	109.8	C11—C10—H10B	109.1
C2—C1—H1B	109.8	H10A—C10—H10B	107.9
H1A—C1—H1B	108.2	C12—C11—C10	111.8 (3)
C3—C2—C1	111.8 (4)	C12—C11—H11A	109.2
C3—C2—H2A	109.3	C10—C11—H11A	109.2
C1—C2—H2A	109.3	C12—C11—H11B	109.2
C3—C2—H2B	109.3	C10—C11—H11B	109.2
C1—C2—H2B	109.3	H11A—C11—H11B	107.9
H2A—C2—H2B	107.9	C11—C12—C7	109.5 (3)
C2—C3—C4	112.2 (4)	C11—C12—H12A	109.8
C2—C3—H3A	109.2	C7—C12—H12A	109.8
C4—C3—H3A	109.2	C11—C12—H12B	109.8
C2—C3—H3B	109.2	C7—C12—H12B	109.8
C4—C3—H3B	109.2	H12A—C12—H12B	108.2
H3A—C3—H3B	107.9	O1—C13—C14	119.97 (15)
C3—C4—C5	109.8 (4)	O1—C13—C18	120.00 (15)
C3—C4—H4A	109.7	C14—C13—C18	120.0
C5—C4—H4A	109.7	C13—C14—C15	120.0
C3—C4—H4B	109.7	C13—C14—Cl1	121.02 (12)
C5—C4—H4B	109.7	C15—C14—Cl1	118.91 (12)
H4A—C4—H4B	108.2	C16—C15—C14	120.0
C6—C5—C4	110.0 (3)	C16—C15—H15	120.0
C6—C5—H5A	109.7	C14—C15—H15	120.0
C4—C5—H5A	109.7	C15—C16—C17	120.0
C6—C5—H5B	109.7	C15—C16—Cl2	120.07 (14)
C4—C5—H5B	109.7	C17—C16—Cl2	119.93 (14)
H5A—C5—H5B	108.2	C18—C17—C16	120.0
N1—C6—C5	112.3 (3)	C18—C17—H17	120.0
N1—C6—C1	108.8 (3)	C16—C17—H17	120.0
C5—C6—C1	112.5 (3)	C17—C18—C13	120.0
N1—C6—H6	107.7	C17—C18—H18	120.0
C5—C6—H6	107.7	C13—C18—H18	120.0
C1—C6—H6	107.7	C20^i—C19—C20	122.4 (6)
N1—C7—C8	107.7 (3)	C20^i—C19—Cl3	118.8 (3)
N1—C7—C12	110.4 (3)	C20—C19—Cl3	118.8 (3)
C8—C7—C12	111.5 (3)	C19—C20—C21	119.2 (4)
N1—C7—H7	109.0	C19—C20—H20	120.4
C8—C7—H7	109.0	C21—C20—H20	120.4
C12—C7—H7	109.0	C20—C21—C22	123.6 (3)
C7—C8—C9	109.3 (3)	C20—C21—Cl4	118.2 (3)
C7—C8—H8A	109.8	C22—C21—Cl4	118.2 (3)
C9—C8—H8A	109.8	O2—C22—C21	124.0 (2)
C7—C8—H8B	109.8	O2—C22—C21^i	124.0 (2)
C9—C8—H8B	109.8	C21—C22—C21^i	112.0 (4)
H8A—C8—H8B	108.3	C6—N1—C7	118.0 (3)
C10—C9—C8	112.3 (4)	C6—N1—H1C	106 (2)
C10—C9—H9A	109.1	C7—N1—H1C	106 (2)
C8—C9—H9A	109.1	C6—N1—H1D	114 (2)
C10—C9—H9B	109.1	C7—N1—H1D	107 (2)
C8—C9—H9B	109.1	H1C—N1—H1D	104 (3)
H9A—C9—H9B	107.9	C13—O1—H1	113.3 (15)
C9—C10—C11	112.3 (4)
C6—C1—C2—C3	55.1 (5)	Cl1—C14—C15—C16	−177.0 (2)
C1—C2—C3—C4	−56.1 (6)	C14—C15—C16—C17	0.0
C2—C3—C4—C5	55.7 (6)	C14—C15—C16—Cl2	−179.8 (2)
C3—C4—C5—C6	−55.7 (5)	C15—C16—C17—C18	0.0
C4—C5—C6—N1	−179.1 (3)	Cl2—C16—C17—C18	179.8 (2)
C4—C5—C6—C1	57.8 (5)	C16—C17—C18—C13	0.0
C2—C1—C6—N1	178.1 (3)	O1—C13—C18—C17	−177.8 (2)
C2—C1—C6—C5	−56.8 (5)	C14—C13—C18—C17	0.0
N1—C7—C8—C9	−179.2 (3)	C20^i—C19—C20—C21	0.9 (2)
C12—C7—C8—C9	−57.9 (4)	Cl3—C19—C20—C21	−179.1 (2)
C7—C8—C9—C10	56.6 (5)	C19—C20—C21—C22	−1.9 (5)
C8—C9—C10—C11	−54.6 (5)	C19—C20—C21—Cl4	−179.4 (2)
C9—C10—C11—C12	53.7 (6)	C20—C21—C22—O2	−179.1 (2)
C10—C11—C12—C7	−53.8 (5)	Cl4—C21—C22—O2	−1.6 (3)
N1—C7—C12—C11	177.1 (3)	C20—C21—C22—C21^i	0.9 (2)
C8—C7—C12—C11	57.4 (4)	Cl4—C21—C22—C21^i	178.4 (3)
O1—C13—C14—C15	177.8 (2)	C5—C6—N1—C7	57.8 (4)
C18—C13—C14—C15	0.0	C1—C6—N1—C7	−177.0 (3)
O1—C13—C14—Cl1	−5.3 (2)	C8—C7—N1—C6	−175.7 (3)
C18—C13—C14—Cl1	176.9 (2)	C12—C7—N1—C6	62.3 (4)
C13—C14—C15—C16	0.0

Symmetry code: (i) −y+1, −x+1, −z+1/4.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1^i	1.22 (3)	1.22 (3)	2.439 (4)	176 (5)
N1—H1C···O2	0.88 (4)	1.85 (4)	2.726 (4)	176 (3)
N1—H1D···O1	0.90 (4)	1.98 (4)	2.868 (4)	170 (3)

Symmetry code: (i) −y+1, −x+1, −z+1/4.