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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229613033810/em3064sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229613033810/em3064Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229613033810/em3064Isup3.cml
Supplementary material

CCDC reference: 977068

Introduction top

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).

Experimental top

Synthesis and crystallization top

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).

Refinement top

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 Uiso(H) = 1.2Ueq of the parent atoms.

Results and discussion top

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 ππ 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 top

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 top

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 top
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 top
Crystal data top
2C12H24N+·C6H3Cl2O·C6H2Cl3O·C6H4Cl2ODx = 1.310 Mg m3
Mr = 886.05Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4122Cell parameters from 2879 reflections
a = 10.604 (1) Åθ = 2.1–23.1°
c = 39.960 (9) ŵ = 0.48 mm1
V = 4493.3 (12) Å3T = 293 K
Z = 4Prism, colorless
F(000) = 18640.34 × 0.32 × 0.30 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
4422 independent reflections
Radiation source: fine-focus sealed tube3563 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
φ and ω scansθmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1213
Tmin = 0.893, Tmax = 0.918k = 913
25411 measured reflectionsl = 4449
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.146 w = 1/[σ2(Fo2) + (0.0916P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
4422 reflectionsΔρmax = 0.33 e Å3
245 parametersΔρmin = 0.32 e Å3
0 restraintsAbsolute structure: Flack & Bernardinelli (1999), 1763 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.00 (9)
Crystal data top
2C12H24N+·C6H3Cl2O·C6H2Cl3O·C6H4Cl2OZ = 4
Mr = 886.05Mo Kα radiation
Tetragonal, P4122µ = 0.48 mm1
a = 10.604 (1) ÅT = 293 K
c = 39.960 (9) Å0.34 × 0.32 × 0.30 mm
V = 4493.3 (12) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
4422 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
3563 reflections with I > 2σ(I)
Tmin = 0.893, Tmax = 0.918Rint = 0.016
25411 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.058H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.146Δρmax = 0.33 e Å3
S = 1.10Δρmin = 0.32 e Å3
4422 reflectionsAbsolute structure: Flack & Bernardinelli (1999), 1763 Friedel pairs
245 parametersAbsolute structure parameter: 0.00 (9)
0 restraints
Special details top

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

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 (Å2) top
xyzUiso*/Ueq
C10.6792 (4)0.5410 (4)0.06619 (8)0.0659 (10)
H1A0.58850.53230.06820.079*
H1B0.71730.45960.07080.079*
C20.7132 (4)0.5833 (5)0.03085 (9)0.0770 (12)
H2A0.68790.51860.01500.092*
H2B0.66700.65970.02550.092*
C30.8515 (4)0.6076 (5)0.02726 (10)0.0828 (13)
H3A0.86850.63820.00480.099*
H3B0.89700.52900.03020.099*
C40.8993 (5)0.7035 (5)0.05254 (9)0.0831 (13)
H4A0.86080.78490.04820.100*
H4B0.98990.71260.05040.100*
C50.8664 (4)0.6600 (4)0.08825 (9)0.0662 (10)
H5A0.91160.58280.09340.079*
H5B0.89210.72390.10420.079*
C60.7266 (3)0.6375 (3)0.09116 (8)0.0514 (8)
H60.68380.71740.08640.062*
C70.7204 (3)0.6820 (3)0.15414 (7)0.0463 (7)
H70.81170.69630.15450.056*
C80.6818 (4)0.6157 (4)0.18605 (8)0.0560 (8)
H8A0.72750.53680.18820.067*
H8B0.59230.59680.18540.067*
C90.7108 (5)0.7006 (5)0.21589 (10)0.0770 (12)
H9A0.68290.65930.23620.092*
H9B0.80130.71260.21750.092*
C100.6497 (5)0.8230 (5)0.21323 (11)0.0921 (15)
H10A0.67600.87540.23180.110*
H10B0.55910.81180.21470.110*
C110.6814 (5)0.8900 (4)0.18044 (10)0.0789 (12)
H11A0.63260.96710.17890.095*
H11B0.77000.91260.18040.095*
C120.6535 (4)0.8080 (3)0.15031 (9)0.0622 (9)
H12A0.68220.84980.13010.075*
H12B0.56330.79450.14840.075*
C130.85606 (19)0.31031 (18)0.16520 (4)0.0455 (7)
C140.9499 (2)0.38293 (17)0.18001 (6)0.0526 (8)
C151.0078 (2)0.3418 (2)0.20925 (6)0.0667 (11)
H151.07050.39040.21910.080*
C160.9719 (2)0.2281 (2)0.22368 (5)0.0701 (11)
C170.8781 (2)0.1555 (2)0.20887 (5)0.0691 (11)
H170.85410.07940.21850.083*
C180.8202 (2)0.19657 (19)0.17964 (5)0.0621 (9)
H180.75740.14800.16970.074*
C190.1591 (4)0.8409 (4)0.12500.0694 (15)
C200.2148 (4)0.8104 (4)0.09596 (10)0.0641 (10)
H200.19240.85150.07630.077*
C210.3062 (4)0.7166 (3)0.09563 (8)0.0559 (9)
C220.3481 (3)0.6519 (3)0.12500.0465 (10)
Cl11.00087 (10)0.51891 (9)0.16186 (3)0.0741 (3)
Cl21.04267 (9)0.17755 (10)0.25968 (2)0.0683 (3)
Cl30.04269 (8)0.95731 (8)0.12500.0675 (4)
Cl40.37592 (10)0.68113 (10)0.05872 (2)0.0688 (3)
N10.6888 (3)0.5968 (3)0.12552 (7)0.0453 (6)
O10.7965 (2)0.3526 (2)0.13720 (5)0.0470 (5)
O20.4336 (2)0.5664 (2)0.12500.0505 (7)
H1C0.606 (3)0.591 (3)0.1252 (8)0.046 (9)*
H1D0.716 (4)0.519 (4)0.1312 (9)0.064 (11)*
H10.725 (3)0.275 (3)0.12500.057 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.069 (2)0.075 (3)0.0541 (19)0.021 (2)0.0072 (18)0.0144 (19)
C20.083 (3)0.100 (3)0.048 (2)0.005 (2)0.005 (2)0.008 (2)
C30.074 (3)0.117 (4)0.057 (2)0.007 (3)0.014 (2)0.001 (2)
C40.080 (3)0.108 (4)0.062 (2)0.028 (3)0.015 (2)0.014 (2)
C50.055 (2)0.083 (3)0.0604 (19)0.0226 (19)0.0091 (18)0.0037 (19)
C60.060 (2)0.0433 (18)0.0512 (17)0.0037 (16)0.0052 (15)0.0025 (15)
C70.0425 (17)0.0433 (17)0.0533 (17)0.0083 (14)0.0029 (13)0.0148 (14)
C80.0506 (19)0.057 (2)0.0609 (19)0.0011 (16)0.0043 (16)0.0020 (17)
C90.079 (3)0.089 (3)0.063 (2)0.012 (2)0.006 (2)0.015 (2)
C100.103 (4)0.092 (3)0.082 (3)0.009 (3)0.019 (3)0.038 (3)
C110.088 (3)0.053 (2)0.095 (3)0.011 (2)0.020 (3)0.031 (2)
C120.064 (2)0.0452 (19)0.077 (2)0.0055 (17)0.0083 (19)0.0032 (18)
C130.0455 (17)0.0385 (15)0.0525 (17)0.0034 (14)0.0028 (14)0.0081 (14)
C140.0394 (16)0.056 (2)0.0624 (19)0.0027 (15)0.0077 (15)0.0131 (17)
C150.0485 (19)0.092 (3)0.060 (2)0.001 (2)0.0134 (17)0.027 (2)
C160.056 (2)0.103 (3)0.052 (2)0.000 (2)0.0150 (18)0.003 (2)
C170.068 (2)0.083 (3)0.056 (2)0.009 (2)0.0137 (18)0.0164 (19)
C180.062 (2)0.058 (2)0.067 (2)0.0139 (18)0.0178 (18)0.0032 (18)
C190.0527 (19)0.0527 (19)0.103 (5)0.009 (2)0.001 (2)0.001 (2)
C200.060 (2)0.053 (2)0.079 (2)0.0129 (18)0.0163 (19)0.0084 (19)
C210.060 (2)0.052 (2)0.0558 (19)0.0215 (17)0.0007 (16)0.0025 (16)
C220.0394 (15)0.0394 (15)0.061 (3)0.0107 (19)0.0040 (13)0.0040 (13)
Cl10.0578 (5)0.0603 (6)0.1041 (8)0.0168 (4)0.0085 (5)0.0097 (5)
Cl20.0635 (5)0.0773 (6)0.0640 (5)0.0151 (5)0.0168 (4)0.0172 (5)
Cl30.0645 (5)0.0645 (5)0.0737 (8)0.0187 (6)0.0077 (5)0.0077 (5)
Cl40.0734 (7)0.0708 (6)0.0621 (5)0.0063 (5)0.0028 (5)0.0035 (5)
N10.0489 (17)0.0412 (15)0.0458 (14)0.0027 (12)0.0050 (13)0.0005 (11)
O10.0545 (13)0.0413 (12)0.0453 (11)0.0058 (10)0.0092 (10)0.0058 (9)
O20.0485 (11)0.0485 (11)0.0545 (18)0.0073 (15)0.0023 (10)0.0023 (10)
Geometric parameters (Å, º) top
C1—C61.515 (5)C10—H10B0.9700
C1—C21.525 (5)C11—C121.514 (5)
C1—H1A0.9700C11—H11A0.9700
C1—H1B0.9700C11—H11B0.9700
C2—C31.497 (6)C12—H12A0.9700
C2—H2A0.9700C12—H12B0.9700
C2—H2B0.9700C13—O11.361 (2)
C3—C41.521 (6)C13—C141.3900
C3—H3A0.9700C13—C181.3900
C3—H3B0.9700C14—C151.3900
C4—C51.540 (5)C14—Cl11.702 (2)
C4—H4A0.9700C15—C161.3900
C4—H4B0.9700C15—H150.9300
C5—C61.506 (5)C16—C171.3900
C5—H5A0.9700C16—Cl21.7087 (17)
C5—H5B0.9700C17—C181.3900
C6—N11.494 (4)C17—H170.9300
C6—H60.9800C18—H180.9300
C7—N11.495 (4)C19—C20i1.342 (5)
C7—C81.513 (5)C19—C201.342 (5)
C7—C121.520 (5)C19—Cl31.745 (6)
C7—H70.9800C20—C211.389 (6)
C8—C91.525 (5)C20—H200.9300
C8—H8A0.9700C21—C221.430 (4)
C8—H8B0.9700C21—Cl41.692 (4)
C9—C101.455 (7)C22—O21.282 (5)
C9—H9A0.9700C22—C21i1.430 (4)
C9—H9B0.9700N1—H1C0.88 (4)
C10—C111.528 (6)N1—H1D0.90 (4)
C10—H10A0.9700O1—H11.22 (3)
C6—C1—C2109.4 (3)C9—C10—H10A109.1
C6—C1—H1A109.8C11—C10—H10A109.1
C2—C1—H1A109.8C9—C10—H10B109.1
C6—C1—H1B109.8C11—C10—H10B109.1
C2—C1—H1B109.8H10A—C10—H10B107.9
H1A—C1—H1B108.2C12—C11—C10111.8 (3)
C3—C2—C1111.8 (4)C12—C11—H11A109.2
C3—C2—H2A109.3C10—C11—H11A109.2
C1—C2—H2A109.3C12—C11—H11B109.2
C3—C2—H2B109.3C10—C11—H11B109.2
C1—C2—H2B109.3H11A—C11—H11B107.9
H2A—C2—H2B107.9C11—C12—C7109.5 (3)
C2—C3—C4112.2 (4)C11—C12—H12A109.8
C2—C3—H3A109.2C7—C12—H12A109.8
C4—C3—H3A109.2C11—C12—H12B109.8
C2—C3—H3B109.2C7—C12—H12B109.8
C4—C3—H3B109.2H12A—C12—H12B108.2
H3A—C3—H3B107.9O1—C13—C14119.97 (15)
C3—C4—C5109.8 (4)O1—C13—C18120.00 (15)
C3—C4—H4A109.7C14—C13—C18120.0
C5—C4—H4A109.7C13—C14—C15120.0
C3—C4—H4B109.7C13—C14—Cl1121.02 (12)
C5—C4—H4B109.7C15—C14—Cl1118.91 (12)
H4A—C4—H4B108.2C16—C15—C14120.0
C6—C5—C4110.0 (3)C16—C15—H15120.0
C6—C5—H5A109.7C14—C15—H15120.0
C4—C5—H5A109.7C15—C16—C17120.0
C6—C5—H5B109.7C15—C16—Cl2120.07 (14)
C4—C5—H5B109.7C17—C16—Cl2119.93 (14)
H5A—C5—H5B108.2C18—C17—C16120.0
N1—C6—C5112.3 (3)C18—C17—H17120.0
N1—C6—C1108.8 (3)C16—C17—H17120.0
C5—C6—C1112.5 (3)C17—C18—C13120.0
N1—C6—H6107.7C17—C18—H18120.0
C5—C6—H6107.7C13—C18—H18120.0
C1—C6—H6107.7C20i—C19—C20122.4 (6)
N1—C7—C8107.7 (3)C20i—C19—Cl3118.8 (3)
N1—C7—C12110.4 (3)C20—C19—Cl3118.8 (3)
C8—C7—C12111.5 (3)C19—C20—C21119.2 (4)
N1—C7—H7109.0C19—C20—H20120.4
C8—C7—H7109.0C21—C20—H20120.4
C12—C7—H7109.0C20—C21—C22123.6 (3)
C7—C8—C9109.3 (3)C20—C21—Cl4118.2 (3)
C7—C8—H8A109.8C22—C21—Cl4118.2 (3)
C9—C8—H8A109.8O2—C22—C21124.0 (2)
C7—C8—H8B109.8O2—C22—C21i124.0 (2)
C9—C8—H8B109.8C21—C22—C21i112.0 (4)
H8A—C8—H8B108.3C6—N1—C7118.0 (3)
C10—C9—C8112.3 (4)C6—N1—H1C106 (2)
C10—C9—H9A109.1C7—N1—H1C106 (2)
C8—C9—H9A109.1C6—N1—H1D114 (2)
C10—C9—H9B109.1C7—N1—H1D107 (2)
C8—C9—H9B109.1H1C—N1—H1D104 (3)
H9A—C9—H9B107.9C13—O1—H1113.3 (15)
C9—C10—C11112.3 (4)
C6—C1—C2—C355.1 (5)Cl1—C14—C15—C16177.0 (2)
C1—C2—C3—C456.1 (6)C14—C15—C16—C170.0
C2—C3—C4—C555.7 (6)C14—C15—C16—Cl2179.8 (2)
C3—C4—C5—C655.7 (5)C15—C16—C17—C180.0
C4—C5—C6—N1179.1 (3)Cl2—C16—C17—C18179.8 (2)
C4—C5—C6—C157.8 (5)C16—C17—C18—C130.0
C2—C1—C6—N1178.1 (3)O1—C13—C18—C17177.8 (2)
C2—C1—C6—C556.8 (5)C14—C13—C18—C170.0
N1—C7—C8—C9179.2 (3)C20i—C19—C20—C210.9 (2)
C12—C7—C8—C957.9 (4)Cl3—C19—C20—C21179.1 (2)
C7—C8—C9—C1056.6 (5)C19—C20—C21—C221.9 (5)
C8—C9—C10—C1154.6 (5)C19—C20—C21—Cl4179.4 (2)
C9—C10—C11—C1253.7 (6)C20—C21—C22—O2179.1 (2)
C10—C11—C12—C753.8 (5)Cl4—C21—C22—O21.6 (3)
N1—C7—C12—C11177.1 (3)C20—C21—C22—C21i0.9 (2)
C8—C7—C12—C1157.4 (4)Cl4—C21—C22—C21i178.4 (3)
O1—C13—C14—C15177.8 (2)C5—C6—N1—C757.8 (4)
C18—C13—C14—C150.0C1—C6—N1—C7177.0 (3)
O1—C13—C14—Cl15.3 (2)C8—C7—N1—C6175.7 (3)
C18—C13—C14—Cl1176.9 (2)C12—C7—N1—C662.3 (4)
C13—C14—C15—C160.0
Symmetry code: (i) y+1, x+1, z+1/4.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O1i1.22 (3)1.22 (3)2.439 (4)176 (5)
N1—H1C···O20.88 (4)1.85 (4)2.726 (4)176 (3)
N1—H1D···O10.90 (4)1.98 (4)2.868 (4)170 (3)
Symmetry code: (i) y+1, x+1, z+1/4.

Experimental details

Crystal data
Chemical formula2C12H24N+·C6H3Cl2O·C6H2Cl3O·C6H4Cl2O
Mr886.05
Crystal system, space groupTetragonal, P4122
Temperature (K)293
a, c (Å)10.604 (1), 39.960 (9)
V3)4493.3 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.48
Crystal size (mm)0.34 × 0.32 × 0.30
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.893, 0.918
No. of measured, independent and
observed [I > 2σ(I)] reflections
25411, 4422, 3563
Rint0.016
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.146, 1.10
No. of reflections4422
No. of parameters245
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.33, 0.32
Absolute structureFlack & Bernardinelli (1999), 1763 Friedel pairs
Absolute structure parameter0.00 (9)

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
C6—N11.494 (4)C20—C211.389 (6)
C7—N11.495 (4)C21—C221.430 (4)
C13—O11.361 (2)C22—O21.282 (5)
C19—C201.342 (5)
C2—C1—C6—N1178.1 (3)C1—C6—N1—C7177.0 (3)
N1—C7—C8—C9179.2 (3)C8—C7—N1—C6175.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O1i1.22 (3)1.22 (3)2.439 (4)176 (5)
N1—H1C···O20.88 (4)1.85 (4)2.726 (4)176 (3)
N1—H1D···O10.90 (4)1.98 (4)2.868 (4)170 (3)
Symmetry code: (i) y+1, x+1, z+1/4.
 

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