Inclusion of chloro­phenols by 4,4′-(cyclo­hexane-1,1-di­yl)diphenol: structures and kinetics of decomposition

The structures of the inclusion compounds 4,4′-(cyclo­hexane-1,1-diyl)diphenol–3-chloro­phenol (1/1) and 4,4′-(cyclo­hex­ane-1,1-diyl)diphenol–4-chloro­phenol (1/1), both C₁₈H₂₀O₂·C₆­H₅ClO, are isostructural with respect to the host mol­ecule and are stabilized by extensive host–host, host–guest and guest–host hydrogen bonding. The packing is characterized by layers of host and guest mol­ecules. The kinetics of thermal decomposition follow the R2 contracting-area model, kt = [1 − (1 − α)^½], and yield activation energies of 105 (8) and 96 (8) kJ mol⁻¹, respectively.

S1. Comment

The host compound 1,1'-bis(4-hydroxyphenyl)cyclohexane forms inclusion compounds with a variety of guests. It enclathrates cyclohexanol and cyclohexanone (Goldberg et al., 1987), as well as phenol and the isomers of cresol (Goldberg et al., 1988). It has been employed to separate several mixtures of isomers, including the phenyl diamines (Caira et al., 1997), the picolines (Caira et al., 1997) and aliphatic alcohols (Caira et al., 1998a or 1998b?). The separation of lutidines and their kinetics of thermal decomposition have been studied (Caira et al., 1998a or 1998b?). We have demonstrated the use of controlled crystallization temperatures to obtain xylidine clathrates with differing host–guest ratios, a phenomenon of current interest (Nassimbeni & Su, 2002; Ibragimov, 2007). We now present the structures of the inclusion compounds formed by this host with m- and p-chlorophenol, (I) and (II), respectively (Figs. 1 and 2, respectively), their thermal characteristics and their kinetics of decomposition.

Compounds (I) and (II) both crystallize in the space group P1 with Z = 2, with similar unit-cell parameters and host–guest ratios of 1:1. They are isostructural with respect to the positions of the host atoms, except for the hydroxyl H atoms, which are located in positions governed by the requirements of the hydrogen bonding. The packing is characterized by ribbons of host molecules running in the [010] direction and linked by (Host)O—H···O(H)(Host) hydrogen bonds. These ribbons are in turn cross-linked by (Host)O—H···O(H)(Guest) and (Guest)O—H···O(H)(Host) hydrogen bonds, running in the [100] direction. The hydrogen-bonding network for (I) is shown in Fig. 3 as an example. Details of the hydrogen bonds for structures (I) and (II) are given in Tables 3 and 4, respectively. Double ribbons of host molecules form layers perpendicular to c, with the guest chlorophenols interleaving the hydrophilic side of the host layers which contain the hydroxyl moieties. This is shown in Fig. 4. The narrowest interlayer host spacing is approximately 2.1 Å for (I) and 2.3 Å for (II). This packing is common for this host and reoccurs in the structures with phenyl diamines (Caira et al., 1997), picolines (Caira et al., 1997), aliphatic alcohols (Caira et al., 1998a or 1998b?) and lutidines (Caira et al., 1998a or 1998b?).

The conformation of the host molecule is governed by the torsion angles C2—C1—C7—C8 and C6—C1—C13—C14, and the dihedral angle between rings C7–C12 and C13–C18. In both structures, the host conformations are very similar (Table 1).

The results of the thermal analysis are given in Table 2. The measured and calculated values for the mass loss are in excellent agreement, confirming the host–guest ratios and justifying the use of full site-occupancy factors for the guest atoms in the crystallographic refinement. Differential scanning calorimetry showed a single endotherm for guest loss for both compounds, and the onset temperatures occur at values well below the normal boiling points of the guests. This is an indication of relatively weak interactions between host and guest.

The kinetics of thermal decomposition were determined for both compounds by performing a series of isothermal thermogravimetric experiments between 363 and 403 K. For both compounds, the plots of the resultant extent of reaction α versus time are deceleratory and fitt the R2 contracting-area model, kt = [1-(1-α)^1/2] (Brown, 1988), over a wide range of α from 0.05 to 0.95. Arrhenius plots of ln k versus 1/T, shown in Fig. 5, yield activation energies of 105 (8) kJ mol^-1 for (I) and 96 (8) kJ mol^-1 for (II).

Related literature

For related literature, see: Brown (1988); Caira et al. (1997, 1998a, 1998b); Goldberg et al. (1987, 1988); Ibragimov (2007); Nassimbeni & Su (2002).

S2. Experimental

The 1,1'-bis(4-hydroxyphenyl)cyclohexane host compound was dissolved in excess amounts of 1:1 (mol/mol) mixtures of ethylacetate and o-chlorophenol, ethylacetate and m-chlorophenol, and ethylacetate and p-chlorophenol. The resultant solutions were allowed to stand open at room temperature. Colourless needle-like crystals appeared after between a few days and a little more than a week. The crystalline products were subjected to thermogravimetry, differential scanning calorimetry and X-ray analysis. The inclusion compounds (I) and (II) were obtained from their respective mother liquors. o-Chlorophenol was not included and the resultant crystals were those of the apohost.

Thermogravimetry and differential scanning calorimetry experiments were performed using a Perkin Elmer PC series System. Programmed analyses were carried out at a heating rate of 10 K min^-1 under a dry nitrogen gas purge with a flow rate of 30 ml min^-1 over a temperature range from 303 to 553 K.

S3. Refinement

For both structures (I) and (II), the host hydroxyl H atoms and the m- and p-chlorophenol hydroxyl H atoms were all located in difference electron-density maps and refined with simple bond-length constraints [Restraints?], O—H = 0.98 (1) Å, and with U_iso(H) refined independently for structure (II), but fixed at 1.5U_iso(O) for structure (I) (due to its relatively high thermal motion). The rest of the H atoms were placed in idealized positions in a riding model, with C—H = 0.95 or 0.99 Å, and refined with U_iso(H) = 1.2U_eq(C).

Computing details

For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001) and ORTEPIII (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme; the suffix G denotes the guest molecule. Displacement ellipsoids are drawn at the 38% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The structure of (II), showing the atom-numbering scheme; the suffix G denotes the guest molecule. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. A partial packing diagram for structure (I), showing the hydrogen-bonding network. Host and guest molecules are represented with dark and light bonds, respectively. All H atoms, except the hydroxyl H atoms, have been omitted for clarity. Hydrogen bonds are shown as dotted lines. [Symmetry codes: (i) x, 1 + y, z; (ii) x - 1, y - 1, z.]
	Fig. 4. A projection of structure (II), viewed along [100], showing the double ribbons of host molecules forming layers perpendicular to c and the guest molecules located between the host layers. All H atoms of the host molecules have been omitted for clarity. The guest p-chlorophenol molecules are represented by their van der Waals radii.
	Fig. 5. Arrhenius plots of ln k versus 1/T for the decomposition reactions of (I) and (II).

(I) 4,4'-(cyclohexane-1,1'-diyl)diphenol–3-chlorophenol (1/1)

Crystal data

C18H20O2·C6H5ClO	Z = 2
Mr = 396.89	F(000) = 420
Triclinic, P1	Dx = 1.325 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2254 (2) Å	Cell parameters from 17364 reflections
b = 10.7538 (3) Å	θ = 2.7–25.4°
c = 15.3703 (6) Å	µ = 0.22 mm^−1
α = 98.214 (1)°	T = 183 K
β = 93.370 (1)°	Needle, colourless
γ = 101.247 (2)°	0.18 × 0.10 × 0.04 mm
V = 994.89 (6) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	3613 independent reflections
Radiation source: fine-focus sealed tube	2527 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
1.2° ϕ scans and ω scans	θmax = 25.4°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −7→7
Tmin = 0.908, Tmax = 0.992	k = −12→12
17286 measured reflections	l = −18→18

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)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.0411P)^2 + 0.3937P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3613 reflections	Δρmax = 0.30 e Å^−3
263 parameters	Δρmin = −0.29 e Å^−3
3 restraints	Extinction correction: SHELXL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.026 (5)

Special details

Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 30 mm; combination of ϕ and ω scans of 1.2°, 25 s per °, 2 iterations.

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
Cl1G	−0.22373 (12)	0.48030 (6)	−0.10639 (4)	0.0533 (2)
O1	0.1818 (3)	1.02947 (13)	0.16119 (10)	0.0331 (4)
O2	−0.0940 (3)	0.19032 (13)	0.19404 (11)	0.0364 (4)
O1G	−0.4693 (3)	0.15251 (16)	0.09114 (11)	0.0450 (5)
H1	0.078 (4)	1.084 (2)	0.1767 (18)	0.068*
H2	−0.232 (3)	0.184 (3)	0.1594 (16)	0.068*
H1G	−0.591 (3)	0.101 (2)	0.1152 (18)	0.068*
C1	0.2352 (3)	0.68141 (18)	0.40738 (13)	0.0245 (5)
C2	0.0916 (3)	0.69468 (19)	0.48593 (14)	0.0272 (5)
H2A	−0.0616	0.6908	0.4625	0.033*
H2B	0.0911	0.6208	0.5178	0.033*
C3	0.1699 (4)	0.8192 (2)	0.55142 (14)	0.0311 (5)
H3A	0.1534	0.8932	0.5219	0.037*
H3B	0.0767	0.8186	0.6014	0.037*
C4	0.4094 (4)	0.8347 (2)	0.58639 (15)	0.0351 (6)
H4A	0.4593	0.9198	0.6236	0.042*
H4B	0.4227	0.7681	0.6235	0.042*
C5	0.5544 (4)	0.8228 (2)	0.51063 (15)	0.0340 (5)
H5A	0.7075	0.8278	0.5346	0.041*
H5B	0.5538	0.8952	0.4775	0.041*
C6	0.4737 (3)	0.69628 (19)	0.44837 (14)	0.0284 (5)
H6A	0.4813	0.6243	0.4812	0.034*
H6B	0.5725	0.6910	0.4004	0.034*
C7	0.2230 (3)	0.78193 (18)	0.34640 (13)	0.0241 (5)
C8	0.0576 (3)	0.85278 (19)	0.34614 (14)	0.0274 (5)
H8	−0.0474	0.8441	0.3885	0.033*
C9	0.0425 (4)	0.93587 (19)	0.28541 (14)	0.0287 (5)
H9	−0.0725	0.9824	0.2863	0.034*
C10	0.1942 (3)	0.95057 (18)	0.22416 (13)	0.0257 (5)
C11	0.3611 (4)	0.88195 (19)	0.22259 (14)	0.0290 (5)
H11	0.4664	0.8919	0.1805	0.035*
C12	0.3730 (3)	0.79888 (19)	0.28279 (14)	0.0274 (5)
H12	0.4872	0.7517	0.2808	0.033*
C13	0.1502 (3)	0.54815 (18)	0.35099 (13)	0.0240 (5)
C14	0.2728 (4)	0.45336 (19)	0.34002 (15)	0.0294 (5)
H14	0.4170	0.4696	0.3688	0.035*
C15	0.1897 (4)	0.3350 (2)	0.28779 (14)	0.0310 (5)
H15	0.2770	0.2716	0.2814	0.037*
C16	−0.0185 (4)	0.30959 (19)	0.24529 (14)	0.0272 (5)
C17	−0.1464 (3)	0.40164 (19)	0.25522 (14)	0.0288 (5)
H17	−0.2911	0.3845	0.2268	0.035*
C18	−0.0603 (3)	0.51919 (19)	0.30724 (14)	0.0284 (5)
H18	−0.1481	0.5824	0.3133	0.034*
C1G	−0.5302 (4)	0.2166 (2)	0.02565 (15)	0.0322 (5)
C2G	−0.3674 (4)	0.3061 (2)	−0.00244 (15)	0.0327 (5)
H2G	−0.2198	0.3219	0.0228	0.039*
C3G	−0.4266 (4)	0.3717 (2)	−0.06824 (15)	0.0347 (6)
C4G	−0.6406 (4)	0.3514 (2)	−0.10498 (15)	0.0397 (6)
H4G	−0.6782	0.3986	−0.1492	0.048*
C5G	−0.7989 (4)	0.2615 (2)	−0.07652 (16)	0.0401 (6)
H5G	−0.9466	0.2467	−0.1016	0.048*
C6G	−0.7456 (4)	0.1924 (2)	−0.01183 (15)	0.0360 (6)
H6G	−0.8550	0.1293	0.0067	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1G	0.0728 (5)	0.0419 (4)	0.0419 (4)	−0.0041 (3)	0.0160 (3)	0.0124 (3)
O1	0.0394 (10)	0.0302 (8)	0.0338 (9)	0.0101 (7)	0.0077 (7)	0.0132 (7)
O2	0.0353 (9)	0.0257 (8)	0.0453 (10)	0.0075 (7)	−0.0096 (8)	−0.0004 (7)
O1G	0.0331 (10)	0.0539 (10)	0.0478 (11)	−0.0031 (8)	−0.0073 (8)	0.0284 (9)
C1	0.0226 (11)	0.0233 (10)	0.0274 (11)	0.0036 (9)	0.0013 (9)	0.0055 (9)
C2	0.0267 (12)	0.0274 (11)	0.0279 (12)	0.0045 (9)	0.0031 (9)	0.0067 (9)
C3	0.0321 (13)	0.0336 (12)	0.0275 (12)	0.0071 (10)	0.0033 (10)	0.0037 (10)
C4	0.0331 (13)	0.0377 (13)	0.0319 (13)	0.0069 (10)	−0.0032 (10)	0.0001 (10)
C5	0.0265 (12)	0.0324 (12)	0.0401 (14)	0.0037 (10)	−0.0037 (10)	0.0014 (10)
C6	0.0259 (12)	0.0287 (11)	0.0311 (12)	0.0069 (9)	0.0009 (9)	0.0056 (9)
C7	0.0224 (11)	0.0224 (10)	0.0266 (11)	0.0038 (9)	0.0015 (9)	0.0025 (8)
C8	0.0272 (12)	0.0295 (11)	0.0269 (12)	0.0076 (9)	0.0060 (9)	0.0056 (9)
C9	0.0299 (12)	0.0259 (11)	0.0322 (12)	0.0101 (9)	0.0028 (10)	0.0049 (9)
C10	0.0307 (12)	0.0214 (10)	0.0235 (11)	0.0023 (9)	−0.0025 (9)	0.0047 (9)
C11	0.0306 (12)	0.0273 (11)	0.0292 (12)	0.0050 (9)	0.0070 (10)	0.0045 (9)
C12	0.0271 (12)	0.0252 (11)	0.0319 (12)	0.0094 (9)	0.0040 (10)	0.0051 (9)
C13	0.0247 (11)	0.0255 (10)	0.0226 (11)	0.0053 (9)	0.0018 (9)	0.0065 (8)
C14	0.0270 (12)	0.0284 (11)	0.0332 (12)	0.0060 (9)	0.0006 (10)	0.0060 (9)
C15	0.0322 (13)	0.0269 (11)	0.0355 (13)	0.0104 (10)	0.0001 (10)	0.0052 (10)
C16	0.0309 (12)	0.0227 (10)	0.0276 (12)	0.0046 (9)	0.0006 (10)	0.0048 (9)
C17	0.0235 (12)	0.0309 (11)	0.0320 (12)	0.0040 (9)	−0.0015 (9)	0.0094 (10)
C18	0.0274 (12)	0.0265 (11)	0.0326 (12)	0.0085 (9)	0.0021 (10)	0.0047 (9)
C1G	0.0337 (13)	0.0340 (12)	0.0285 (12)	0.0046 (10)	−0.0019 (10)	0.0087 (10)
C2G	0.0310 (13)	0.0345 (12)	0.0308 (12)	0.0030 (10)	0.0007 (10)	0.0049 (10)
C3G	0.0491 (16)	0.0270 (12)	0.0269 (12)	0.0043 (11)	0.0101 (11)	0.0023 (10)
C4G	0.0577 (17)	0.0361 (13)	0.0278 (13)	0.0167 (12)	0.0008 (12)	0.0052 (10)
C5G	0.0397 (15)	0.0456 (14)	0.0335 (13)	0.0124 (12)	−0.0048 (11)	−0.0001 (11)
C6G	0.0327 (14)	0.0366 (13)	0.0351 (13)	0.0000 (10)	−0.0012 (11)	0.0047 (11)

Geometric parameters (Å, º)

Cl1G—C3G	1.735 (2)	C8—H8	0.9500
O1—C10	1.383 (2)	C9—C10	1.376 (3)
O1—H1	0.968 (10)	C9—H9	0.9500
O2—C16	1.385 (2)	C10—C11	1.386 (3)
O2—H2	0.970 (10)	C11—C12	1.383 (3)
O1G—C1G	1.374 (3)	C11—H11	0.9500
O1G—H1G	0.972 (10)	C12—H12	0.9500
C1—C7	1.538 (3)	C13—C14	1.386 (3)
C1—C13	1.543 (3)	C13—C18	1.394 (3)
C1—C6	1.548 (3)	C14—C15	1.391 (3)
C1—C2	1.551 (3)	C14—H14	0.9500
C2—C3	1.532 (3)	C15—C16	1.376 (3)
C2—H2A	0.9900	C15—H15	0.9500
C2—H2B	0.9900	C16—C17	1.384 (3)
C3—C4	1.524 (3)	C17—C18	1.386 (3)
C3—H3A	0.9900	C17—H17	0.9500
C3—H3B	0.9900	C18—H18	0.9500
C4—C5	1.521 (3)	C1G—C6G	1.389 (3)
C4—H4A	0.9900	C1G—C2G	1.389 (3)
C4—H4B	0.9900	C2G—C3G	1.385 (3)
C5—C6	1.525 (3)	C2G—H2G	0.9500
C5—H5A	0.9900	C3G—C4G	1.380 (3)
C5—H5B	0.9900	C4G—C5G	1.377 (3)
C6—H6A	0.9900	C4G—H4G	0.9500
C6—H6B	0.9900	C5G—C6G	1.385 (3)
C7—C8	1.396 (3)	C5G—H5G	0.9500
C7—C12	1.398 (3)	C6G—H6G	0.9500
C8—C9	1.393 (3)
C10—O1—H1	109.5 (17)	C8—C9—H9	120.0
C16—O2—H2	113.3 (16)	C9—C10—O1	121.83 (18)
C1G—O1G—H1G	114.6 (17)	C9—C10—C11	119.92 (19)
C7—C1—C13	107.09 (16)	O1—C10—C11	118.21 (19)
C7—C1—C6	110.46 (17)	C12—C11—C10	119.5 (2)
C13—C1—C6	111.77 (16)	C12—C11—H11	120.3
C7—C1—C2	112.95 (16)	C10—C11—H11	120.3
C13—C1—C2	108.42 (16)	C11—C12—C7	122.30 (19)
C6—C1—C2	106.21 (17)	C11—C12—H12	118.8
C3—C2—C1	113.77 (17)	C7—C12—H12	118.8
C3—C2—H2A	108.8	C14—C13—C18	116.83 (19)
C1—C2—H2A	108.8	C14—C13—C1	123.63 (19)
C3—C2—H2B	108.8	C18—C13—C1	119.54 (17)
C1—C2—H2B	108.8	C13—C14—C15	121.5 (2)
H2A—C2—H2B	107.7	C13—C14—H14	119.2
C4—C3—C2	111.52 (17)	C15—C14—H14	119.2
C4—C3—H3A	109.3	C16—C15—C14	120.22 (19)
C2—C3—H3A	109.3	C16—C15—H15	119.9
C4—C3—H3B	109.3	C14—C15—H15	119.9
C2—C3—H3B	109.3	C15—C16—C17	119.88 (19)
H3A—C3—H3B	108.0	C15—C16—O2	118.09 (18)
C5—C4—C3	110.66 (18)	C17—C16—O2	122.03 (19)
C5—C4—H4A	109.5	C16—C17—C18	119.0 (2)
C3—C4—H4A	109.5	C16—C17—H17	120.5
C5—C4—H4B	109.5	C18—C17—H17	120.5
C3—C4—H4B	109.5	C17—C18—C13	122.50 (19)
H4A—C4—H4B	108.1	C17—C18—H18	118.7
C4—C5—C6	111.08 (18)	C13—C18—H18	118.7
C4—C5—H5A	109.4	O1G—C1G—C6G	121.5 (2)
C6—C5—H5A	109.4	O1G—C1G—C2G	117.5 (2)
C4—C5—H5B	109.4	C6G—C1G—C2G	121.0 (2)
C6—C5—H5B	109.4	C3G—C2G—C1G	118.1 (2)
H5A—C5—H5B	108.0	C3G—C2G—H2G	121.0
C5—C6—C1	112.70 (17)	C1G—C2G—H2G	121.0
C5—C6—H6A	109.1	C4G—C3G—C2G	121.9 (2)
C1—C6—H6A	109.1	C4G—C3G—Cl1G	119.46 (18)
C5—C6—H6B	109.1	C2G—C3G—Cl1G	118.65 (19)
C1—C6—H6B	109.1	C5G—C4G—C3G	119.0 (2)
H6A—C6—H6B	107.8	C5G—C4G—H4G	120.5
C8—C7—C12	116.62 (19)	C3G—C4G—H4G	120.5
C8—C7—C1	123.34 (18)	C4G—C5G—C6G	120.9 (2)
C12—C7—C1	119.87 (18)	C4G—C5G—H5G	119.6
C9—C8—C7	121.7 (2)	C6G—C5G—H5G	119.6
C9—C8—H8	119.2	C5G—C6G—C1G	119.1 (2)
C7—C8—H8	119.2	C5G—C6G—H6G	120.4
C10—C9—C8	120.00 (19)	C1G—C6G—H6G	120.4
C10—C9—H9	120.0
C7—C1—C2—C3	−66.0 (2)	C7—C1—C13—C14	122.0 (2)
C13—C1—C2—C3	175.53 (17)	C6—C1—C13—C14	0.9 (3)
C6—C1—C2—C3	55.3 (2)	C2—C1—C13—C14	−115.8 (2)
C1—C2—C3—C4	−55.5 (2)	C7—C1—C13—C18	−57.3 (2)
C2—C3—C4—C5	53.5 (2)	C6—C1—C13—C18	−178.44 (18)
C3—C4—C5—C6	−55.6 (2)	C2—C1—C13—C18	64.8 (2)
C4—C5—C6—C1	59.5 (2)	C18—C13—C14—C15	0.0 (3)
C7—C1—C6—C5	65.7 (2)	C1—C13—C14—C15	−179.37 (19)
C13—C1—C6—C5	−175.13 (17)	C13—C14—C15—C16	0.1 (3)
C2—C1—C6—C5	−57.1 (2)	C14—C15—C16—C17	−0.6 (3)
C13—C1—C7—C8	102.2 (2)	C14—C15—C16—O2	−179.97 (19)
C6—C1—C7—C8	−135.9 (2)	C15—C16—C17—C18	0.9 (3)
C2—C1—C7—C8	−17.1 (3)	O2—C16—C17—C18	−179.78 (19)
C13—C1—C7—C12	−72.9 (2)	C16—C17—C18—C13	−0.7 (3)
C6—C1—C7—C12	49.1 (2)	C14—C13—C18—C17	0.3 (3)
C2—C1—C7—C12	167.86 (18)	C1—C13—C18—C17	179.70 (19)
C12—C7—C8—C9	0.2 (3)	O1G—C1G—C2G—C3G	−179.82 (19)
C1—C7—C8—C9	−175.05 (19)	C6G—C1G—C2G—C3G	0.7 (3)
C7—C8—C9—C10	−0.6 (3)	C1G—C2G—C3G—C4G	0.8 (3)
C8—C9—C10—O1	178.24 (18)	C1G—C2G—C3G—Cl1G	−178.09 (16)
C8—C9—C10—C11	0.4 (3)	C2G—C3G—C4G—C5G	−1.3 (3)
C9—C10—C11—C12	0.1 (3)	Cl1G—C3G—C4G—C5G	177.61 (17)
O1—C10—C11—C12	−177.75 (18)	C3G—C4G—C5G—C6G	0.2 (3)
C10—C11—C12—C7	−0.6 (3)	C4G—C5G—C6G—C1G	1.3 (3)
C8—C7—C12—C11	0.4 (3)	O1G—C1G—C6G—C5G	178.8 (2)
C1—C7—C12—C11	175.81 (18)	C2G—C1G—C6G—C5G	−1.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	0.97 (1)	1.72 (1)	2.684 (2)	173 (3)
O2—H2···O1G	0.97 (1)	1.71 (1)	2.672 (2)	172 (3)
O1G—H1G···O1^ii	0.97 (1)	1.71 (1)	2.681 (2)	172 (3)

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

(II) 4,4'-(cyclohexane-1,1'-diyl)diphenol–4-chlorophenol (1/1)

Crystal data

C18H20O2·C6H5ClO	Z = 2
Mr = 396.89	F(000) = 420
Triclinic, P1	Dx = 1.312 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2593 (2) Å	Cell parameters from 19130 reflections
b = 10.8408 (3) Å	θ = 3.5–25.6°
c = 15.6476 (6) Å	µ = 0.21 mm^−1
α = 99.705 (1)°	T = 183 K
β = 92.366 (1)°	Needle, colourless
γ = 105.376 (2)°	0.20 × 0.12 × 0.08 mm
V = 1004.99 (6) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	3773 independent reflections
Radiation source: fine-focus sealed tube	2425 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
1.2° ϕ scans and ω scans	θmax = 25.6°, θmin = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −7→7
Tmin = 0.913, Tmax = 0.983	k = −13→13
19130 measured reflections	l = −18→18

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)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.119	w = 1/[σ^2(Fo^2) + (0.0469P)^2 + 0.3889P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3773 reflections	Δρmax = 0.42 e Å^−3
263 parameters	Δρmin = −0.51 e Å^−3
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (3)

Special details

Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 30 mm; combination of ϕ and ω scans of 1.2°, 20 s per °, 2 iterations.

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
Cl1G	−0.49130 (17)	0.47375 (8)	−0.14954 (5)	0.0706 (3)
O1	0.1592 (3)	1.01169 (15)	0.16817 (10)	0.0336 (4)
O2	−0.1069 (3)	0.16836 (15)	0.19171 (11)	0.0361 (4)
O1G	−0.4800 (3)	0.10776 (16)	0.08643 (11)	0.0369 (4)
H1	0.288 (3)	1.037 (3)	0.1359 (15)	0.055*
H2	−0.004 (4)	0.116 (2)	0.1871 (18)	0.055*
H1G	−0.341 (3)	0.135 (2)	0.1228 (15)	0.055*
C1	0.2437 (3)	0.6740 (2)	0.40556 (14)	0.0234 (5)
C2	0.1018 (4)	0.6845 (2)	0.48388 (14)	0.0269 (5)
H2A	−0.0537	0.6739	0.4617	0.032*
H2B	0.1017	0.6123	0.5151	0.032*
C3	0.1846 (4)	0.8136 (2)	0.54827 (15)	0.0303 (5)
H3A	0.1687	0.8856	0.5194	0.036*
H3B	0.0921	0.8118	0.5981	0.036*
C4	0.4268 (4)	0.8383 (2)	0.58141 (16)	0.0351 (6)
H4A	0.4396	0.7732	0.6173	0.042*
H4B	0.4798	0.9258	0.6186	0.042*
C5	0.5718 (4)	0.8297 (2)	0.50583 (16)	0.0331 (6)
H5A	0.5721	0.9009	0.4736	0.040*
H5B	0.7267	0.8404	0.5287	0.040*
C6	0.4848 (3)	0.6990 (2)	0.44437 (15)	0.0275 (5)
H6A	0.4926	0.6287	0.4764	0.033*
H6B	0.5823	0.6956	0.3963	0.033*
C7	0.2276 (3)	0.7720 (2)	0.34586 (14)	0.0230 (5)
C8	0.0569 (4)	0.8323 (2)	0.34645 (15)	0.0279 (5)
H8	−0.0483	0.8185	0.3884	0.034*
C9	0.0356 (4)	0.9120 (2)	0.28772 (15)	0.0294 (5)
H9	−0.0830	0.9515	0.2895	0.035*
C10	0.1879 (4)	0.9334 (2)	0.22686 (14)	0.0253 (5)
C11	0.3609 (4)	0.8768 (2)	0.22497 (15)	0.0273 (5)
H11	0.4671	0.8923	0.1836	0.033*
C12	0.3787 (4)	0.7971 (2)	0.28400 (14)	0.0257 (5)
H12	0.4983	0.7582	0.2821	0.031*
C13	0.1568 (3)	0.5367 (2)	0.34958 (14)	0.0241 (5)
C14	0.2764 (4)	0.4450 (2)	0.34032 (15)	0.0275 (5)
H14	0.4200	0.4667	0.3706	0.033*
C15	0.1933 (4)	0.3225 (2)	0.28819 (15)	0.0291 (5)
H15	0.2800	0.2622	0.2829	0.035*
C16	−0.0152 (4)	0.2889 (2)	0.24423 (14)	0.0275 (5)
C17	−0.1410 (4)	0.3773 (2)	0.25284 (15)	0.0318 (6)
H17	−0.2860	0.3544	0.2236	0.038*
C18	−0.0539 (4)	0.4986 (2)	0.30420 (15)	0.0304 (6)
H18	−0.1409	0.5588	0.3089	0.036*
C1G	−0.4784 (4)	0.1930 (2)	0.03017 (14)	0.0302 (6)
C2G	−0.2835 (4)	0.2781 (2)	0.01503 (15)	0.0346 (6)
H2G	−0.1457	0.2781	0.0429	0.041*
C3G	−0.2893 (5)	0.3640 (2)	−0.04122 (16)	0.0418 (7)
H3G	−0.1550	0.4221	−0.0524	0.050*
C4G	−0.4884 (5)	0.3650 (2)	−0.08052 (16)	0.0409 (7)
C5G	−0.6832 (5)	0.2779 (3)	−0.06724 (17)	0.0460 (7)
H5G	−0.8202	0.2771	−0.0961	0.055*
C6G	−0.6788 (4)	0.1913 (3)	−0.01149 (16)	0.0400 (6)
H6G	−0.8128	0.1313	−0.0020	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1G	0.1394 (8)	0.0534 (5)	0.0385 (4)	0.0546 (5)	0.0096 (4)	0.0172 (4)
O1	0.0385 (10)	0.0342 (10)	0.0365 (10)	0.0160 (8)	0.0068 (8)	0.0188 (8)
O2	0.0385 (10)	0.0262 (9)	0.0429 (10)	0.0140 (7)	−0.0106 (8)	−0.0003 (8)
O1G	0.0346 (10)	0.0393 (10)	0.0363 (10)	0.0048 (8)	−0.0033 (7)	0.0157 (8)
C1	0.0209 (11)	0.0232 (12)	0.0274 (12)	0.0060 (9)	0.0023 (9)	0.0081 (10)
C2	0.0251 (12)	0.0267 (12)	0.0294 (13)	0.0048 (9)	0.0017 (10)	0.0107 (10)
C3	0.0312 (13)	0.0322 (13)	0.0281 (13)	0.0085 (10)	0.0047 (10)	0.0068 (11)
C4	0.0345 (14)	0.0342 (14)	0.0335 (14)	0.0078 (11)	−0.0054 (11)	0.0026 (11)
C5	0.0256 (12)	0.0307 (13)	0.0401 (15)	0.0052 (10)	−0.0054 (11)	0.0043 (11)
C6	0.0240 (12)	0.0286 (13)	0.0329 (13)	0.0087 (10)	0.0016 (10)	0.0117 (11)
C7	0.0208 (11)	0.0201 (11)	0.0261 (12)	0.0035 (9)	−0.0015 (9)	0.0031 (10)
C8	0.0231 (12)	0.0314 (13)	0.0319 (13)	0.0085 (10)	0.0059 (10)	0.0108 (11)
C9	0.0244 (12)	0.0315 (13)	0.0366 (14)	0.0129 (10)	0.0042 (10)	0.0095 (11)
C10	0.0308 (13)	0.0212 (12)	0.0245 (12)	0.0067 (10)	−0.0009 (10)	0.0077 (10)
C11	0.0294 (12)	0.0267 (13)	0.0276 (13)	0.0096 (10)	0.0072 (10)	0.0054 (10)
C12	0.0252 (12)	0.0261 (12)	0.0295 (12)	0.0125 (9)	0.0036 (10)	0.0065 (10)
C13	0.0229 (11)	0.0251 (12)	0.0261 (12)	0.0055 (9)	0.0037 (9)	0.0113 (10)
C14	0.0231 (12)	0.0283 (13)	0.0328 (13)	0.0082 (10)	−0.0009 (10)	0.0097 (11)
C15	0.0283 (13)	0.0261 (13)	0.0368 (14)	0.0118 (10)	0.0004 (10)	0.0100 (11)
C16	0.0309 (13)	0.0223 (12)	0.0292 (13)	0.0069 (10)	−0.0011 (10)	0.0063 (10)
C17	0.0257 (13)	0.0308 (14)	0.0379 (14)	0.0083 (10)	−0.0069 (10)	0.0051 (12)
C18	0.0265 (13)	0.0281 (13)	0.0377 (14)	0.0107 (10)	−0.0023 (10)	0.0051 (11)
C1G	0.0357 (14)	0.0322 (14)	0.0245 (12)	0.0123 (11)	0.0011 (10)	0.0056 (11)
C2G	0.0349 (14)	0.0358 (14)	0.0330 (14)	0.0094 (11)	−0.0006 (11)	0.0080 (12)
C3G	0.0555 (17)	0.0339 (15)	0.0347 (15)	0.0089 (12)	0.0061 (13)	0.0079 (12)
C4G	0.070 (2)	0.0361 (15)	0.0253 (14)	0.0290 (14)	0.0068 (13)	0.0056 (12)
C5G	0.0535 (18)	0.0624 (19)	0.0337 (15)	0.0390 (15)	−0.0019 (13)	0.0057 (14)
C6G	0.0325 (14)	0.0522 (17)	0.0376 (15)	0.0151 (12)	−0.0005 (11)	0.0099 (13)

Geometric parameters (Å, º)

Cl1G—C4G	1.731 (2)	C8—H8	0.9500
O1—C10	1.388 (3)	C9—C10	1.379 (3)
O1—H1	0.971 (10)	C9—H9	0.9500
O2—C16	1.383 (3)	C10—C11	1.378 (3)
O2—H2	0.963 (10)	C11—C12	1.387 (3)
O1G—C1G	1.378 (3)	C11—H11	0.9500
O1G—H1G	0.968 (10)	C12—H12	0.9500
C1—C13	1.539 (3)	C13—C14	1.388 (3)
C1—C6	1.540 (3)	C13—C18	1.396 (3)
C1—C7	1.548 (3)	C14—C15	1.390 (3)
C1—C2	1.549 (3)	C14—H14	0.9500
C2—C3	1.529 (3)	C15—C16	1.378 (3)
C2—H2A	0.9900	C15—H15	0.9500
C2—H2B	0.9900	C16—C17	1.386 (3)
C3—C4	1.520 (3)	C17—C18	1.379 (3)
C3—H3A	0.9900	C17—H17	0.9500
C3—H3B	0.9900	C18—H18	0.9500
C4—C5	1.526 (3)	C1G—C2G	1.377 (3)
C4—H4A	0.9900	C1G—C6G	1.384 (3)
C4—H4B	0.9900	C2G—C3G	1.391 (3)
C5—C6	1.522 (3)	C2G—H2G	0.9500
C5—H5A	0.9900	C3G—C4G	1.370 (4)
C5—H5B	0.9900	C3G—H3G	0.9500
C6—H6A	0.9900	C4G—C5G	1.377 (4)
C6—H6B	0.9900	C5G—C6G	1.390 (4)
C7—C12	1.390 (3)	C5G—H5G	0.9500
C7—C8	1.392 (3)	C6G—H6G	0.9500
C8—C9	1.388 (3)
C10—O1—H1	112.8 (16)	C8—C9—H9	120.2
C16—O2—H2	111.8 (16)	C11—C10—C9	120.1 (2)
C1G—O1G—H1G	109.7 (16)	C11—C10—O1	121.9 (2)
C13—C1—C6	111.31 (17)	C9—C10—O1	117.98 (19)
C13—C1—C7	107.00 (16)	C10—C11—C12	119.5 (2)
C6—C1—C7	110.99 (17)	C10—C11—H11	120.3
C13—C1—C2	108.95 (17)	C12—C11—H11	120.3
C6—C1—C2	106.28 (17)	C11—C12—C7	122.2 (2)
C7—C1—C2	112.35 (17)	C11—C12—H12	118.9
C3—C2—C1	113.64 (18)	C7—C12—H12	118.9
C3—C2—H2A	108.8	C14—C13—C18	116.2 (2)
C1—C2—H2A	108.8	C14—C13—C1	123.91 (19)
C3—C2—H2B	108.8	C18—C13—C1	119.90 (19)
C1—C2—H2B	108.8	C13—C14—C15	122.2 (2)
H2A—C2—H2B	107.7	C13—C14—H14	118.9
C4—C3—C2	111.23 (19)	C15—C14—H14	118.9
C4—C3—H3A	109.4	C16—C15—C14	119.8 (2)
C2—C3—H3A	109.4	C16—C15—H15	120.1
C4—C3—H3B	109.4	C14—C15—H15	120.1
C2—C3—H3B	109.4	C15—C16—O2	122.38 (19)
H3A—C3—H3B	108.0	C15—C16—C17	119.6 (2)
C3—C4—C5	110.88 (19)	O2—C16—C17	117.97 (19)
C3—C4—H4A	109.5	C18—C17—C16	119.4 (2)
C5—C4—H4A	109.5	C18—C17—H17	120.3
C3—C4—H4B	109.5	C16—C17—H17	120.3
C5—C4—H4B	109.5	C17—C18—C13	122.7 (2)
H4A—C4—H4B	108.1	C17—C18—H18	118.7
C6—C5—C4	110.53 (19)	C13—C18—H18	118.7
C6—C5—H5A	109.5	C2G—C1G—O1G	121.5 (2)
C4—C5—H5A	109.5	C2G—C1G—C6G	120.2 (2)
C6—C5—H5B	109.5	O1G—C1G—C6G	118.4 (2)
C4—C5—H5B	109.5	C1G—C2G—C3G	119.7 (2)
H5A—C5—H5B	108.1	C1G—C2G—H2G	120.1
C5—C6—C1	113.14 (18)	C3G—C2G—H2G	120.1
C5—C6—H6A	109.0	C4G—C3G—C2G	120.1 (3)
C1—C6—H6A	109.0	C4G—C3G—H3G	119.9
C5—C6—H6B	109.0	C2G—C3G—H3G	119.9
C1—C6—H6B	109.0	C3G—C4G—C5G	120.4 (2)
H6A—C6—H6B	107.8	C3G—C4G—Cl1G	119.2 (2)
C12—C7—C8	116.6 (2)	C5G—C4G—Cl1G	120.4 (2)
C12—C7—C1	120.33 (18)	C4G—C5G—C6G	119.9 (2)
C8—C7—C1	122.9 (2)	C4G—C5G—H5G	120.1
C9—C8—C7	122.1 (2)	C6G—C5G—H5G	120.1
C9—C8—H8	119.0	C1G—C6G—C5G	119.7 (3)
C7—C8—H8	119.0	C1G—C6G—H6G	120.1
C10—C9—C8	119.5 (2)	C5G—C6G—H6G	120.1
C10—C9—H9	120.2
C13—C1—C2—C3	175.43 (17)	C6—C1—C13—C14	3.9 (3)
C6—C1—C2—C3	55.4 (2)	C7—C1—C13—C14	125.3 (2)
C7—C1—C2—C3	−66.2 (2)	C2—C1—C13—C14	−113.0 (2)
C1—C2—C3—C4	−55.9 (2)	C6—C1—C13—C18	−175.9 (2)
C2—C3—C4—C5	54.0 (3)	C7—C1—C13—C18	−54.5 (3)
C3—C4—C5—C6	−55.5 (3)	C2—C1—C13—C18	67.2 (2)
C4—C5—C6—C1	59.2 (2)	C18—C13—C14—C15	0.7 (3)
C13—C1—C6—C5	−175.61 (18)	C1—C13—C14—C15	−179.1 (2)
C7—C1—C6—C5	65.3 (2)	C13—C14—C15—C16	−0.5 (3)
C2—C1—C6—C5	−57.1 (2)	C14—C15—C16—O2	−179.8 (2)
C13—C1—C7—C12	−74.6 (2)	C14—C15—C16—C17	−0.4 (3)
C6—C1—C7—C12	47.0 (3)	C15—C16—C17—C18	1.1 (3)
C2—C1—C7—C12	165.83 (19)	O2—C16—C17—C18	−179.5 (2)
C13—C1—C7—C8	100.9 (2)	C16—C17—C18—C13	−0.9 (4)
C6—C1—C7—C8	−137.5 (2)	C14—C13—C18—C17	0.0 (3)
C2—C1—C7—C8	−18.6 (3)	C1—C13—C18—C17	179.8 (2)
C12—C7—C8—C9	0.9 (3)	O1G—C1G—C2G—C3G	−179.0 (2)
C1—C7—C8—C9	−174.8 (2)	C6G—C1G—C2G—C3G	1.1 (4)
C7—C8—C9—C10	−0.3 (3)	C1G—C2G—C3G—C4G	0.8 (4)
C8—C9—C10—C11	−0.6 (3)	C2G—C3G—C4G—C5G	−2.4 (4)
C8—C9—C10—O1	178.9 (2)	C2G—C3G—C4G—Cl1G	179.48 (19)
C9—C10—C11—C12	0.8 (3)	C3G—C4G—C5G—C6G	2.1 (4)
O1—C10—C11—C12	−178.6 (2)	Cl1G—C4G—C5G—C6G	−179.83 (19)
C10—C11—C12—C7	−0.2 (3)	C2G—C1G—C6G—C5G	−1.4 (4)
C8—C7—C12—C11	−0.6 (3)	O1G—C1G—C6G—C5G	178.7 (2)
C1—C7—C12—C11	175.2 (2)	C4G—C5G—C6G—C1G	−0.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O1G^i	0.97 (1)	1.73 (1)	2.695 (2)	170 (2)
O2—H2···O1^ii	0.96 (1)	1.71 (1)	2.671 (2)	173 (3)
O1G—H1G···O2	0.97 (1)	1.70 (1)	2.665 (2)	174 (2)

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