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The crystal structures of the title compounds (both C7H7ClO) are characterized by two independent mol­ecules in each of the asymmetric units and feature O—H...O, C—H...π and π–π interactions. In addition, intermolecular C—H...Cl and intramolecular O—H...Cl interactions are present in 2-chloro-5-methyl­phenol. For each crystal, the non-covalent interactions emphasize the different spatial environments for the two independent mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103012447/bm1535sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103012447/bm1535Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103012447/bm1535IIsup3.hkl
Contains datablock II

CCDC references: 221087; 221088

Comment top

4-Chloro-3-methylphenol (chlorocresol), (II), is a common antibacterial and anti-fungal agent that is used widely as a preservative in skin creams (BNF, 2003). It can be detected and quantified by a variety of analytical methods, including HPLC (Gatti et al., 1997). Neither the crystal structure of (II) nor that of the structural isomer 2-chloro-5-methylphenol, (I), has been reported previously.

There are an increasing number of publications on non-covalent interactions, such as hydrogen bonding (Desiraju, 1996; Jeffrey, 1997; Desiraju & Steiner, 1999), and as these small aromatic molecules are planar it is the determination of the supramolecular structure that is of interest.

Both compounds crystallize in space group P21/c, with similar unit-cell volumes, and each has two independent molecules in the unit cell. The atomic arrangements in the molecules are shown in Figs. 1 and 2.

Bond lengths, valence angles and torsion angles [Table 1 for (I) and Table 5 for (II)] are as expected for these chloromethylphenols. Very small differences between the geometries of the two independent molecules in each asymmetric unit are ascribed to the differences in non-covalent interactions at each molecule.

In (I), short H···Cl intramolecular and intermolecular attractions (Aullón et al., 1998; Aakeroy et al., 1999; Brammer et al., 2001) are present. An intramolecular O—H···Cl interaction stabilizes the molecular structure, and the O—H···Cl—C torsion angles in the two independent molecules are 22 (2)° (unprimed atoms) and −23 (2)° (primed atoms). Other geometric parameters of this intramolecular hydrogen bond are shown in Table 1. In addition, the displacements of atoms H1 and H1' from the planes of the benzene rings are −0.28 (3) and 0.30 (3) Å, respectively, which demonstrates a conformational difference between the two independent molecules in (I). If this was the only non-covalent interaction associated with the O atom, the H atoms might be expected to lie in the planes of the benzene rings, pointing towards the 3py orbital of the Cl. There is also only a small indication of shortening of the C—O bond in (I) compared with (II), where there are no O—H···Cl interactions. In addition, weak, but nearly linear, C6—H6···Cl1 and C6'—H6'···Cl1' interactions are present (Table 1).

The shortest Cl···Cl separations in (I) and (II) are 3.573 (2) and 4.775 (1) Å, respectively, while the sum of the van der Waals radii (Bondi, 1964) is 3.50 Å. The role of Cl···Cl contacts in crystal engineering has been discussed previously (Sarma & Desiraju, 1985; Csöregh et al., 2001).

The molecular-packing diagrams of (I) (Fig. 3) and (II) (Fig. 4) show that the molecules pack in a head-to-tail fashion, forming sheets of molecules running parallel to the c axis. Classical O—H···O hydrogen bonding is present and the geometric parameters are given in Tables 2 and 6. Figs. 5 and 6 show that in both (I) and (II) the O atom acts as a donor and an acceptor, and this is also found in the closely related chloroxylenol molecule (Cox, 1995), where Z' = 2. If the H···Cl contacts in (I) are considered as hydrogen bonds then eight-membered R44(8) rings are formed and bifurcated hydrogen bonding is present at atoms H1 and H1'.

Both supramolecular structures are supported by edge-to-face C—H···π interactions (also known as T-shaped conformations), and the geometric parameters are given in Tables 3 and 7. The differences between the two independent molecules in both crystals are clearly shown. The C—H···π interactions that involve both molecules in (I) are not identical. Similarly, for (II), only one of the two moleucles is involved in these interactions.

Aromatic π···π stacking interactions (Janiak, 2000) are also present in both isomers, as shown in Tables 4 and 8. Fig. 7 shows the stacking of the rings about centres of symmetry. The interplanar separation between the aromatic rings for the unprimed atoms in (II) is 3.422 (2) Å, but the offset of the Cg1···Cg1 ring centres is 3.10 Å. Direct overlap is unfavourable and a small offset is desirable, but as this distance is greater than the length of the benzene ring, π···π interaction is absent. Again, this observation shows the differences between the environments of the independent molecules in (II).

The crystal structure of a complex containing the 4-chloro-3-methylphenol molecule has been published previously (Iimura et al., 1999).

Experimental top

Both compounds were purchased from Sigma-Aldrich and recrystallized from ethanol.

Refinement top

Non-methyl H atoms were initially placed in calculated positions and thereafter were allowed to refine freely, with independent isotropic displacement parameters. Methyl H atoms were located from difference maps and allowed to ride on their attached atoms (C—H = 0.98 Å), with independent isotropic displacement parameters.

Computing details top

For both compounds, data collection: DENZO (Otwinowski and Minor, 1997), COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SIR97 (Altomare et al.,1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997).

Figures top
[Figure 1] Fig. 1. The atomic arrangement in 2-chloro-5-methylphenol. Displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. The atomic arrangement in 3-chloro-4-methylphenol. Displacement ellipsoids are shown at the 50% probability level.
[Figure 3] Fig. 3. The molecular packing in 2-chloro-5-methylphenol.
[Figure 4] Fig. 4. The molecular packing in 3-chloro-4-methylphenol.
[Figure 5] Fig. 5. Part of the molecular packing for 2-chloro-5-methylphenol, showing O—H···O, O—H···Cl and C—H···Cl interactions. Atoms marked with an asterisk (*) or hash (#) are at the symmetry positions (x,0.5 − y,-0.5 + z) and (x,0.5 − y,0.5 + z), respectively.
[Figure 6] Fig. 6. Part of the molecular packing for 3-chloro-4-methylphenol, showing O—H···O bonding. Atoms marked with an asterisk (*) or hash (#) are at the symmetry positions (x − 1,y,z) and (x − 1,0.5 − y,0.5 + z), respectively.
[Figure 7] Fig. 7. Part of the molecular packing for 2-chloro-5-methylphenol, showing the π···π interactions, as thin lines, between molecules stacked across centres of symmetry.
(I) 2-chloro-methylphenol top
Crystal data top
C7H7ClOF(000) = 592
Mr = 142.58Dx = 1.443 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.951 (3) ÅCell parameters from 8054 reflections
b = 11.430 (2) Åθ = 2.9–27.5°
c = 9.4079 (19) ŵ = 0.49 mm1
β = 109.51 (3)°T = 120 K
V = 1312.7 (5) Å3Block, colourless
Z = 80.40 × 0.32 × 0.26 mm
Data collection top
Enraf Nonius KappaCCD area detector
diffractometer
2998 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode2571 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.088
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
ϕ and ω scans to fill Ewald sphereh = 1516
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
k = 1414
Tmin = 0.560, Tmax = 0.882l = 1211
11902 measured reflections
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)] = 0.056H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.138 w = 1/[σ2(Fo2) + (0.0613P)2 + 1.6312P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
2998 reflectionsΔρmax = 0.81 e Å3
204 parametersΔρmin = 0.44 e Å3
1 restraintExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.047 (5)
Crystal data top
C7H7ClOV = 1312.7 (5) Å3
Mr = 142.58Z = 8
Monoclinic, P21/cMo Kα radiation
a = 12.951 (3) ŵ = 0.49 mm1
b = 11.430 (2) ÅT = 120 K
c = 9.4079 (19) Å0.40 × 0.32 × 0.26 mm
β = 109.51 (3)°
Data collection top
Enraf Nonius KappaCCD area detector
diffractometer
2998 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
2571 reflections with I > 2σ(I)
Tmin = 0.560, Tmax = 0.882Rint = 0.088
11902 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0561 restraint
wR(F2) = 0.138H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.81 e Å3
2998 reflectionsΔρmin = 0.44 e Å3
204 parameters
Special details top

Experimental. Please note cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range.

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 (Å2) top
xyzUiso*/Ueq
Cl10.16014 (5)0.01787 (5)0.18332 (7)0.0212 (2)
O10.19902 (13)0.23504 (16)0.38084 (18)0.0182 (4)
H10.226 (3)0.222 (3)0.308 (3)0.033 (9)*
C10.10363 (18)0.1745 (2)0.3610 (2)0.0143 (5)
C20.07338 (19)0.0738 (2)0.2745 (2)0.0162 (5)
C30.0242 (2)0.0167 (2)0.2614 (3)0.0175 (5)
H30.043 (2)0.054 (3)0.200 (3)0.019 (7)*
C40.09196 (19)0.0606 (2)0.3364 (3)0.0177 (5)
H40.155 (3)0.017 (3)0.329 (4)0.032 (9)*
C50.06305 (18)0.1609 (2)0.4255 (2)0.0151 (5)
C60.03510 (18)0.2173 (2)0.4364 (2)0.0147 (5)
H60.056 (2)0.289 (3)0.497 (3)0.020 (7)*
C70.13535 (19)0.2094 (2)0.5082 (3)0.0192 (5)
H7A0.18320.27000.44660.083 (16)*
H7B0.08970.24320.60430.075 (14)*
H7C0.18020.14630.52740.064 (13)*
Cl1'0.36669 (5)0.01486 (5)0.54728 (6)0.0189 (2)
O1'0.32528 (13)0.23876 (17)0.69276 (19)0.0182 (4)
H1'0.304 (3)0.224 (3)0.603 (4)0.021 (8)*
C1'0.41745 (18)0.1761 (2)0.7707 (2)0.0139 (5)
C2'0.44838 (18)0.0724 (2)0.7197 (2)0.0149 (5)
C3'0.5434 (2)0.0147 (2)0.8043 (3)0.0180 (5)
H3'0.563 (3)0.055 (3)0.769 (3)0.022 (7)*
C4'0.60782 (19)0.0610 (2)0.9417 (3)0.0172 (5)
H4'0.672 (3)0.023 (3)1.002 (4)0.022 (8)*
C5'0.57763 (18)0.1643 (2)0.9966 (2)0.0150 (5)
C6'0.48231 (18)0.2211 (2)0.9098 (3)0.0153 (5)
H6'0.462 (2)0.293 (3)0.948 (3)0.014 (7)*
C7'0.64563 (19)0.2137 (2)1.1474 (3)0.0187 (5)
H7X0.63710.29901.14620.069 (14)*
H7Y0.72290.19411.16750.044 (10)*
H7Z0.62110.18031.22660.053 (12)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0235 (3)0.0217 (4)0.0214 (3)0.0042 (2)0.0115 (2)0.0018 (2)
O10.0137 (8)0.0233 (9)0.0192 (8)0.0038 (7)0.0076 (6)0.0027 (7)
C10.0123 (10)0.0170 (11)0.0125 (10)0.0005 (8)0.0028 (8)0.0024 (8)
C20.0171 (11)0.0174 (12)0.0144 (10)0.0043 (9)0.0054 (8)0.0022 (9)
C30.0188 (12)0.0140 (11)0.0175 (11)0.0008 (8)0.0032 (9)0.0005 (8)
C40.0144 (11)0.0176 (12)0.0193 (11)0.0020 (9)0.0032 (9)0.0022 (9)
C50.0134 (10)0.0171 (11)0.0142 (10)0.0025 (8)0.0039 (8)0.0034 (8)
C60.0145 (11)0.0158 (11)0.0128 (10)0.0005 (8)0.0031 (8)0.0007 (8)
C70.0155 (11)0.0225 (13)0.0210 (11)0.0007 (9)0.0080 (9)0.0010 (9)
Cl1'0.0196 (3)0.0180 (3)0.0182 (3)0.0027 (2)0.0051 (2)0.0030 (2)
O1'0.0150 (8)0.0241 (9)0.0146 (8)0.0052 (7)0.0037 (6)0.0015 (7)
C1'0.0108 (10)0.0170 (11)0.0154 (10)0.0004 (8)0.0066 (8)0.0036 (8)
C2'0.0148 (11)0.0158 (11)0.0156 (10)0.0028 (8)0.0071 (8)0.0008 (8)
C3'0.0169 (12)0.0159 (12)0.0234 (12)0.0019 (9)0.0096 (10)0.0008 (9)
C4'0.0134 (11)0.0197 (12)0.0193 (11)0.0031 (9)0.0065 (9)0.0041 (9)
C5'0.0131 (10)0.0182 (11)0.0159 (10)0.0012 (8)0.0076 (8)0.0018 (9)
C6'0.0148 (11)0.0170 (12)0.0164 (10)0.0006 (8)0.0083 (8)0.0001 (9)
C7'0.0148 (11)0.0244 (13)0.0165 (11)0.0003 (9)0.0045 (8)0.0001 (9)
Geometric parameters (Å, º) top
Cl1—C21.746 (2)Cl1'—C2'1.743 (2)
O1—C11.373 (3)O1'—C1'1.375 (3)
O1—H10.880 (18)O1'—H1'0.81 (3)
C1—C21.389 (3)C1'—C2'1.386 (3)
C1—C61.397 (3)C1'—C6'1.396 (3)
C2—C31.391 (3)C2'—C3'1.389 (3)
C3—C41.390 (4)C3'—C4'1.388 (4)
C3—H30.98 (3)C3'—H3'0.93 (3)
C4—C51.396 (3)C4'—C5'1.396 (3)
C4—H40.94 (4)C4'—H4'0.94 (3)
C5—C61.398 (3)C5'—C6'1.392 (3)
C5—C71.508 (3)C5'—C7'1.507 (3)
C6—H60.98 (3)C6'—H6'0.97 (3)
C7—H7A0.9800C7'—H7X0.9800
C7—H7B0.9800C7'—H7Y0.9800
C7—H7C0.9800C7'—H7Z0.9800
C1—O1—H1113 (2)C1'—O1'—H1'112 (2)
O1—C1—C2124.2 (2)O1'—C1'—C2'124.1 (2)
O1—C1—C6116.7 (2)O1'—C1'—C6'116.8 (2)
C2—C1—C6119.1 (2)C2'—C1'—C6'119.1 (2)
C1—C2—C3120.7 (2)C1'—C2'—C3'120.7 (2)
C1—C2—Cl1119.31 (18)C1'—C2'—Cl1'119.26 (18)
C3—C2—Cl1119.97 (19)C3'—C2'—Cl1'120.01 (18)
C2—C3—C4119.7 (2)C2'—C3'—C4'119.6 (2)
C2—C3—H3119.0 (18)C2'—C3'—H3'119.6 (19)
C4—C3—H3121.3 (18)C4'—C3'—H3'120.7 (19)
C3—C4—C5120.9 (2)C3'—C4'—C5'120.8 (2)
C3—C4—H4117 (2)C3'—C4'—H4'121.4 (19)
C5—C4—H4122 (2)C5'—C4'—H4'117.8 (19)
C4—C5—C6118.5 (2)C6'—C5'—C4'118.7 (2)
C4—C5—C7121.5 (2)C6'—C5'—C7'120.2 (2)
C6—C5—C7119.9 (2)C4'—C5'—C7'121.2 (2)
C1—C6—C5121.2 (2)C5'—C6'—C1'121.1 (2)
C1—C6—H6119.1 (18)C5'—C6'—H6'118.4 (16)
C5—C6—H6119.8 (18)C1'—C6'—H6'120.5 (16)
C5—C7—H7A109.5C5'—C7'—H7X109.5
C5—C7—H7B109.5C5'—C7'—H7Y109.5
H7A—C7—H7B109.5H7X—C7'—H7Y109.5
C5—C7—H7C109.5C5'—C7'—H7Z109.5
H7A—C7—H7C109.5H7X—C7'—H7Z109.5
H7B—C7—H7C109.5H7Y—C7'—H7Z109.5
O1—C1—C2—C3179.3 (2)O1'—C1'—C2'—C3'179.3 (2)
C6—C1—C2—C30.7 (3)C6'—C1'—C2'—C3'1.0 (3)
O1—C1—C2—Cl10.0 (3)O1'—C1'—C2'—Cl1'0.5 (3)
C6—C1—C2—Cl1178.57 (16)C6'—C1'—C2'—Cl1'179.16 (17)
C1—C2—C3—C40.4 (4)C1'—C2'—C3'—C4'0.3 (4)
Cl1—C2—C3—C4178.87 (18)Cl1'—C2'—C3'—C4'179.81 (18)
C2—C3—C4—C50.4 (4)C2'—C3'—C4'—C5'0.6 (4)
C3—C4—C5—C60.7 (3)C3'—C4'—C5'—C6'0.9 (3)
C3—C4—C5—C7179.7 (2)C3'—C4'—C5'—C7'178.6 (2)
O1—C1—C6—C5178.96 (19)C4'—C5'—C6'—C1'0.2 (3)
C2—C1—C6—C50.3 (3)C7'—C5'—C6'—C1'179.2 (2)
C4—C5—C6—C10.4 (3)O1'—C1'—C6'—C5'179.6 (2)
C7—C5—C6—C1180.0 (2)C2'—C1'—C6'—C5'0.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl10.88 (2)2.62 (3)3.040 (2)110 (3)
O1—H1···Cl10.81 (3)2.64 (4)3.033 (2)112 (3)
C6—H6···Cl1i0.98 (3)2.86 (3)3.830 (3)169 (2)
C6—H6···Cl1i0.97 (3)2.83 (3)3.784 (3)170 (2)
O1—H1···O1ii0.88 (2)1.99 (2)2.798 (2)152 (3)
O1—H1···O10.81 (3)2.09 (3)2.843 (3)155 (3)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.
(II) 4-chloro-3-methylphenol top
Crystal data top
C7H7ClOF(000) = 592
Mr = 142.58Dx = 1.422 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.6998 (4) ÅCell parameters from 36420 reflections
b = 14.2926 (5) Åθ = 2.9–27.5°
c = 8.7105 (3) ŵ = 0.48 mm1
β = 91.152 (2)°T = 120 K
V = 1331.81 (8) Å3Block, colourless
Z = 80.18 × 0.14 × 0.10 mm
Data collection top
Enraf Nonius KappaCCD area detector
diffractometer
3003 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode2032 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.068
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.3°
ϕ and ω scans to fill Ewald sphereh = 1313
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
k = 1818
Tmin = 0.982, Tmax = 1.000l = 1111
15691 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0583P)2]
where P = (Fo2 + 2Fc2)/3
3003 reflections(Δ/σ)max < 0.001
203 parametersΔρmax = 0.34 e Å3
2 restraintsΔρmin = 0.35 e Å3
Crystal data top
C7H7ClOV = 1331.81 (8) Å3
Mr = 142.58Z = 8
Monoclinic, P21/cMo Kα radiation
a = 10.6998 (4) ŵ = 0.48 mm1
b = 14.2926 (5) ÅT = 120 K
c = 8.7105 (3) Å0.18 × 0.14 × 0.10 mm
β = 91.152 (2)°
Data collection top
Enraf Nonius KappaCCD area detector
diffractometer
3003 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
2032 reflections with I > 2σ(I)
Tmin = 0.982, Tmax = 1.000Rint = 0.068
15691 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0462 restraints
wR(F2) = 0.113H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.34 e Å3
3003 reflectionsΔρmin = 0.35 e Å3
203 parameters
Special details top

Experimental. Please note cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range.

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 (Å2) top
xyzUiso*/Ueq
Cl10.73208 (5)0.12767 (4)0.46204 (6)0.03134 (19)
O10.19307 (13)0.18011 (10)0.53937 (16)0.0232 (4)
H10.170 (3)0.2119 (19)0.620 (3)0.068 (10)*
C10.32058 (19)0.16947 (15)0.5274 (2)0.0202 (5)
C20.3617 (2)0.11236 (15)0.4106 (2)0.0206 (5)
H20.299 (2)0.0829 (15)0.345 (3)0.022 (6)*
C30.4885 (2)0.09894 (14)0.3857 (2)0.0211 (5)
C40.57215 (19)0.14412 (15)0.4861 (2)0.0227 (5)
C50.5316 (2)0.20121 (15)0.6030 (3)0.0254 (5)
H50.593 (2)0.2317 (16)0.674 (3)0.031 (6)*
C60.4051 (2)0.21434 (15)0.6239 (2)0.0238 (5)
H60.379 (2)0.2513 (17)0.706 (3)0.030 (6)*
C70.5318 (2)0.03937 (16)0.2558 (2)0.0256 (5)
H7A0.45930.01790.19490.050 (8)*
H7B0.57740.01490.29690.039 (7)*
H7C0.58700.07600.19060.039 (7)*
Cl1'0.75758 (5)0.08351 (4)0.03907 (6)0.03047 (18)
O1'1.08233 (14)0.22045 (11)0.26419 (16)0.0246 (4)
H1'1.117 (2)0.211 (2)0.354 (2)0.061 (9)*
C1'1.00649 (19)0.14708 (15)0.2160 (2)0.0215 (5)
C2'0.9290 (2)0.16333 (17)0.0904 (2)0.0232 (5)
H2'0.929 (2)0.2227 (17)0.044 (3)0.025 (6)*
C3'0.8510 (2)0.09351 (15)0.0316 (2)0.0238 (5)
C4'0.85427 (19)0.00723 (16)0.1058 (2)0.0242 (5)
C5'0.9316 (2)0.00946 (18)0.2315 (3)0.0263 (5)
H5'0.930 (2)0.0669 (17)0.275 (3)0.027 (6)*
C6'1.0083 (2)0.06104 (16)0.2883 (3)0.0246 (5)
H6'1.063 (2)0.0497 (17)0.371 (3)0.032 (6)*
C7'0.7678 (2)0.11282 (17)0.1062 (3)0.0309 (6)
H7X0.77840.06320.18250.056 (8)*
H7Y0.79040.17320.15110.043 (7)*
H7Z0.68040.11460.07460.048 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0204 (3)0.0362 (4)0.0374 (3)0.0008 (2)0.0029 (2)0.0024 (3)
O10.0219 (8)0.0268 (9)0.0210 (8)0.0022 (7)0.0027 (7)0.0020 (7)
C10.0215 (11)0.0192 (11)0.0198 (10)0.0015 (9)0.0013 (9)0.0054 (9)
C20.0223 (11)0.0203 (12)0.0192 (11)0.0016 (9)0.0027 (10)0.0025 (9)
C30.0240 (11)0.0185 (12)0.0209 (11)0.0013 (9)0.0020 (9)0.0040 (9)
C40.0202 (11)0.0237 (12)0.0243 (11)0.0002 (9)0.0018 (9)0.0030 (9)
C50.0269 (12)0.0231 (13)0.0262 (12)0.0030 (10)0.0014 (10)0.0021 (10)
C60.0282 (12)0.0223 (12)0.0210 (11)0.0022 (10)0.0019 (10)0.0033 (9)
C70.0245 (11)0.0290 (13)0.0235 (11)0.0040 (10)0.0024 (10)0.0036 (10)
Cl1'0.0264 (3)0.0285 (3)0.0367 (3)0.0047 (2)0.0047 (3)0.0081 (2)
O1'0.0224 (8)0.0296 (9)0.0216 (8)0.0056 (7)0.0022 (7)0.0010 (7)
C1'0.0168 (10)0.0250 (12)0.0229 (11)0.0016 (9)0.0045 (9)0.0023 (9)
C2'0.0222 (11)0.0245 (13)0.0230 (11)0.0015 (10)0.0026 (9)0.0013 (10)
C3'0.0200 (11)0.0280 (13)0.0235 (11)0.0014 (9)0.0042 (9)0.0029 (9)
C4'0.0191 (10)0.0276 (13)0.0261 (12)0.0024 (9)0.0056 (9)0.0071 (10)
C5'0.0233 (11)0.0258 (14)0.0299 (13)0.0001 (10)0.0058 (10)0.0024 (11)
C6'0.0195 (11)0.0334 (14)0.0211 (11)0.0011 (10)0.0023 (10)0.0030 (10)
C7'0.0301 (13)0.0330 (14)0.0292 (12)0.0007 (11)0.0071 (11)0.0041 (11)
Geometric parameters (Å, º) top
Cl1—C41.744 (2)Cl1'—C4'1.751 (2)
O1—C11.379 (2)O1'—C1'1.386 (2)
O1—H10.877 (17)O1'—H1'0.870 (17)
C1—C61.380 (3)C1'—C2'1.379 (3)
C1—C21.383 (3)C1'—C6'1.381 (3)
C2—C31.392 (3)C2'—C3'1.391 (3)
C2—H20.97 (2)C2'—H2'0.94 (2)
C3—C41.397 (3)C3'—C4'1.392 (3)
C3—C71.497 (3)C3'—C7'1.505 (3)
C4—C51.382 (3)C4'—C5'1.380 (3)
C5—C61.383 (3)C5'—C6'1.385 (3)
C5—H50.99 (2)C5'—H5'0.91 (2)
C6—H60.94 (2)C6'—H6'0.93 (3)
C7—H7A0.9800C7'—H7X0.9800
C7—H7B0.9800C7'—H7Y0.9800
C7—H7C0.9800C7'—H7Z0.9800
C1—O1—H1114 (2)C1'—O1'—H1'112.8 (19)
O1—C1—C2116.79 (18)C2'—C1'—C6'120.9 (2)
O1—C1—C6122.64 (18)C2'—C1'—O1'116.87 (19)
C6—C1—C2120.6 (2)C6'—C1'—O1'122.19 (19)
C1—C2—C3121.4 (2)C1'—C2'—C3'121.2 (2)
C1—C2—H2117.9 (12)C1'—C2'—H2'119.2 (14)
C3—C2—H2120.6 (12)C3'—C2'—H2'119.7 (14)
C2—C3—C4116.92 (19)C2'—C3'—C4'117.1 (2)
C2—C3—C7120.9 (2)C2'—C3'—C7'120.2 (2)
C4—C3—C7122.15 (19)C4'—C3'—C7'122.8 (2)
C5—C4—C3121.9 (2)C5'—C4'—C3'122.0 (2)
C5—C4—Cl1119.43 (17)C5'—C4'—Cl1'118.44 (18)
C3—C4—Cl1118.70 (16)C3'—C4'—Cl1'119.54 (17)
C4—C5—C6120.0 (2)C4'—C5'—C6'120.0 (2)
C4—C5—H5120.4 (13)C4'—C5'—H5'118.4 (15)
C6—C5—H5119.5 (13)C6'—C5'—H5'121.6 (15)
C1—C6—C5119.2 (2)C1'—C6'—C5'118.8 (2)
C1—C6—H6121.4 (14)C1'—C6'—H6'120.6 (15)
C5—C6—H6119.3 (14)C5'—C6'—H6'120.5 (15)
C3—C7—H7A109.5C3'—C7'—H7X109.5
C3—C7—H7B109.5C3'—C7'—H7Y109.5
H7A—C7—H7B109.5H7X—C7'—H7Y109.5
C3—C7—H7C109.5C3'—C7'—H7Z109.5
H7A—C7—H7C109.5H7X—C7'—H7Z109.5
H7B—C7—H7C109.5H7Y—C7'—H7Z109.5
O1—C1—C2—C3178.17 (18)C6'—C1'—C2'—C3'0.6 (3)
C6—C1—C2—C30.6 (3)O1'—C1'—C2'—C3'178.80 (18)
C1—C2—C3—C41.4 (3)C1'—C2'—C3'—C4'0.5 (3)
C1—C2—C3—C7178.04 (19)C1'—C2'—C3'—C7'179.7 (2)
C2—C3—C4—C51.4 (3)C2'—C3'—C4'—C5'0.5 (3)
C7—C3—C4—C5178.08 (19)C7'—C3'—C4'—C5'179.7 (2)
C2—C3—C4—Cl1178.73 (15)C2'—C3'—C4'—Cl1'179.41 (15)
C7—C3—C4—Cl11.8 (3)C7'—C3'—C4'—Cl1'0.5 (3)
C3—C4—C5—C60.5 (3)C3'—C4'—C5'—C6'0.6 (3)
Cl1—C4—C5—C6179.58 (17)Cl1'—C4'—C5'—C6'179.30 (15)
O1—C1—C6—C5179.01 (19)C2'—C1'—C6'—C5'0.7 (3)
C2—C1—C6—C50.3 (3)O1'—C1'—C6'—C5'178.68 (17)
C4—C5—C6—C10.3 (3)C4'—C5'—C6'—C1'0.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O1i0.88 (2)1.85 (2)2.711 (2)165 (3)
O1—H1···O1ii0.87 (2)1.85 (2)2.714 (2)175 (3)
Symmetry codes: (i) x1, y+1/2, z+1/2; (ii) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC7H7ClOC7H7ClO
Mr142.58142.58
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/c
Temperature (K)120120
a, b, c (Å)12.951 (3), 11.430 (2), 9.4079 (19)10.6998 (4), 14.2926 (5), 8.7105 (3)
β (°) 109.51 (3) 91.152 (2)
V3)1312.7 (5)1331.81 (8)
Z88
Radiation typeMo KαMo Kα
µ (mm1)0.490.48
Crystal size (mm)0.40 × 0.32 × 0.260.18 × 0.14 × 0.10
Data collection
DiffractometerEnraf Nonius KappaCCD area detector
diffractometer
Enraf Nonius KappaCCD area detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995, 1997)
Multi-scan
(SORTAV; Blessing, 1995, 1997)
Tmin, Tmax0.560, 0.8820.982, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
11902, 2998, 2571 15691, 3003, 2032
Rint0.0880.068
(sin θ/λ)max1)0.6490.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.138, 1.10 0.046, 0.113, 1.03
No. of reflections29983003
No. of parameters204203
No. of restraints12
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.81, 0.440.34, 0.35

Computer programs: DENZO (Otwinowski and Minor, 1997), COLLECT (Hooft, 1998), DENZO and COLLECT, SIR97 (Altomare et al.,1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997).

Selected geometric parameters (Å, º) for (I) top
Cl1—C21.746 (2)Cl1'—C2'1.743 (2)
O1—C11.373 (3)O1'—C1'1.375 (3)
C5—C71.508 (3)C5'—C7'1.507 (3)
O1—C1—C2124.2 (2)O1'—C1'—C2'124.1 (2)
O1—C1—C6116.7 (2)O1'—C1'—C6'116.8 (2)
C1—C2—Cl1119.31 (18)C1'—C2'—Cl1'119.26 (18)
O1—C1—C2—Cl10.0 (3)O1'—C1'—C2'—Cl1'0.5 (3)
C6—C1—C2—Cl1178.57 (16)C6'—C1'—C2'—Cl1'179.16 (17)
Cl1—C2—C3—C4178.87 (18)Cl1'—C2'—C3'—C4'179.81 (18)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl10.88 (2)2.62 (3)3.040 (2)110 (3)
O1'—H1'···Cl1'0.81 (3)2.64 (4)3.033 (2)112 (3)
C6—H6···Cl1i0.98 (3)2.86 (3)3.830 (3)169 (2)
C6'—H6'···Cl1'i0.97 (3)2.83 (3)3.784 (3)170 (2)
O1—H1···O1'ii0.88 (2)1.99 (2)2.798 (2)152 (3)
O1'—H1'···O10.81 (3)2.09 (3)2.843 (3)155 (3)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.
C—H···π interactions (Å, °) for 2-chloro-5-methylphenol top
C—HCg(I)symmetryH···Cg(I)C—H···Cg(I)C···Cg(I)
C4—H41-x,-y,1 − z3.37 (4)87 (2)3.453 (3)
C7—H7B1x,0.5 − y,0.5 + z2.731663.692 (3)
C7'—H7X2x,0.5 − y,0.5 + z3.091123.579 (3)
C7'—H7Z2x,0.5 − y,0.5 + z3.151083.579 (3)
Cg is the centre of gravity of the aromatic rings: 1: unprimed atoms, 2: primed atoms. The symmetry applies to the Cg(I) position.
π - π interactions (Å, °) for 2-chloro-5-methylphenol top
Cg(I)Cg(J)symmetryCg···Cgdihedral_angleinterplanaroffset
11-x,-y,1 − z3.941 (2)0.03.387 (2)2.02
221 − x,-y,2 − z3.904 (2)0.03.461 (2)1.81
Cg is the centre of gravity of the rings: 1: unprimed atoms, 2: primed atoms The symmetry applies to the Cg(J) position.
Selected geometric parameters (Å, º) for (II) top
Cl1—C41.744 (2)Cl1'—C4'1.751 (2)
O1—C11.379 (2)O1'—C1'1.386 (2)
C3—C71.497 (3)C3'—C7'1.505 (3)
O1—C1—C2116.79 (18)C2'—C1'—O1'116.87 (19)
O1—C1—C6122.64 (18)C6'—C1'—O1'122.19 (19)
C5—C4—Cl1119.43 (17)C5'—C4'—Cl1'118.44 (18)
C1—C2—C3—C7178.04 (19)C1'—C2'—C3'—C7'179.7 (2)
C7—C3—C4—Cl11.8 (3)C7'—C3'—C4'—Cl1'0.5 (3)
Cl1—C4—C5—C6179.58 (17)Cl1'—C4'—C5'—C6'179.30 (15)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O1'i0.877 (17)1.854 (19)2.711 (2)165 (3)
O1'—H1'···O1ii0.870 (17)1.846 (18)2.714 (2)175 (3)
Symmetry codes: (i) x1, y+1/2, z+1/2; (ii) x+1, y, z.
C—H···π interactions (Å, °) for 4-chloro-3-methylphenol top
C—HCg(I)symmetryH···Cg(I)C—H···Cg(I)C···Cg(I)
C6—H61x,0.5 − y,0.5 + z3.00 (3)147 (2)3.823 (3)
C7—H7B11 − x,-y,1 − z2.671413.492 (3)
Cg(1) is the centre of gravity of the aromatic ring (unprimed atoms). The symmetry applies to the Cg(I) position.
π - π interactions (Å, °) for 4-chloro-3-methylphenol top
Cg(I)Cg(J)symmetryCg···Cgdihedral_angleinterplanaroffset
222 − x,-y,-z3.885 (2)0.03.500 (2)1.69
Cg(2) is the centre of gravity of the aromatic ring (primed atoms). The symmetry applies to the Cg(J) position.
 

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