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The crystal structures of the title compounds (both C
7H
7ClO) 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
CCDC references: 221087; 221088
Both compounds were purchased from Sigma-Aldrich and recrystallized from ethanol.
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.
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).
(I) 2-chloro-methylphenol
top
Crystal data top
C7H7ClO | F(000) = 592 |
Mr = 142.58 | Dx = 1.443 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.951 (3) Å | Cell parameters from 8054 reflections |
b = 11.430 (2) Å | θ = 2.9–27.5° |
c = 9.4079 (19) Å | µ = 0.49 mm−1 |
β = 109.51 (3)° | T = 120 K |
V = 1312.7 (5) Å3 | Block, colourless |
Z = 8 | 0.40 × 0.32 × 0.26 mm |
Data collection top
Enraf Nonius KappaCCD area detector diffractometer | 2998 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 2571 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.088 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans to fill Ewald sphere | h = −15→16 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | k = −14→14 |
Tmin = 0.560, Tmax = 0.882 | l = −12→11 |
11902 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.056 | H 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 reflections | Δρmax = 0.81 e Å−3 |
204 parameters | Δρmin = −0.44 e Å−3 |
1 restraint | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.047 (5) |
Crystal data top
C7H7ClO | V = 1312.7 (5) Å3 |
Mr = 142.58 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.951 (3) Å | µ = 0.49 mm−1 |
b = 11.430 (2) Å | T = 120 K |
c = 9.4079 (19) Å | 0.40 × 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 = 0.882 | Rint = 0.088 |
11902 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.056 | 1 restraint |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.81 e Å−3 |
2998 reflections | Δρmin = −0.44 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Cl1 | 0.16014 (5) | 0.01787 (5) | 0.18332 (7) | 0.0212 (2) | |
O1 | 0.19902 (13) | 0.23504 (16) | 0.38084 (18) | 0.0182 (4) | |
H1 | 0.226 (3) | 0.222 (3) | 0.308 (3) | 0.033 (9)* | |
C1 | 0.10363 (18) | 0.1745 (2) | 0.3610 (2) | 0.0143 (5) | |
C2 | 0.07338 (19) | 0.0738 (2) | 0.2745 (2) | 0.0162 (5) | |
C3 | −0.0242 (2) | 0.0167 (2) | 0.2614 (3) | 0.0175 (5) | |
H3 | −0.043 (2) | −0.054 (3) | 0.200 (3) | 0.019 (7)* | |
C4 | −0.09196 (19) | 0.0606 (2) | 0.3364 (3) | 0.0177 (5) | |
H4 | −0.155 (3) | 0.017 (3) | 0.329 (4) | 0.032 (9)* | |
C5 | −0.06305 (18) | 0.1609 (2) | 0.4255 (2) | 0.0151 (5) | |
C6 | 0.03510 (18) | 0.2173 (2) | 0.4364 (2) | 0.0147 (5) | |
H6 | 0.056 (2) | 0.289 (3) | 0.497 (3) | 0.020 (7)* | |
C7 | −0.13535 (19) | 0.2094 (2) | 0.5082 (3) | 0.0192 (5) | |
H7A | −0.1832 | 0.2700 | 0.4466 | 0.083 (16)* | |
H7B | −0.0897 | 0.2432 | 0.6043 | 0.075 (14)* | |
H7C | −0.1802 | 0.1463 | 0.5274 | 0.064 (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) | |
H7X | 0.6371 | 0.2990 | 1.1462 | 0.069 (14)* | |
H7Y | 0.7229 | 0.1941 | 1.1675 | 0.044 (10)* | |
H7Z | 0.6211 | 0.1803 | 1.2266 | 0.053 (12)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0235 (3) | 0.0217 (4) | 0.0214 (3) | 0.0042 (2) | 0.0115 (2) | −0.0018 (2) |
O1 | 0.0137 (8) | 0.0233 (9) | 0.0192 (8) | −0.0038 (7) | 0.0076 (6) | −0.0027 (7) |
C1 | 0.0123 (10) | 0.0170 (11) | 0.0125 (10) | 0.0005 (8) | 0.0028 (8) | 0.0024 (8) |
C2 | 0.0171 (11) | 0.0174 (12) | 0.0144 (10) | 0.0043 (9) | 0.0054 (8) | 0.0022 (9) |
C3 | 0.0188 (12) | 0.0140 (11) | 0.0175 (11) | 0.0008 (8) | 0.0032 (9) | −0.0005 (8) |
C4 | 0.0144 (11) | 0.0176 (12) | 0.0193 (11) | −0.0020 (9) | 0.0032 (9) | 0.0022 (9) |
C5 | 0.0134 (10) | 0.0171 (11) | 0.0142 (10) | 0.0025 (8) | 0.0039 (8) | 0.0034 (8) |
C6 | 0.0145 (11) | 0.0158 (11) | 0.0128 (10) | 0.0005 (8) | 0.0031 (8) | 0.0007 (8) |
C7 | 0.0155 (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—C2 | 1.746 (2) | Cl1'—C2' | 1.743 (2) |
O1—C1 | 1.373 (3) | O1'—C1' | 1.375 (3) |
O1—H1 | 0.880 (18) | O1'—H1' | 0.81 (3) |
C1—C2 | 1.389 (3) | C1'—C2' | 1.386 (3) |
C1—C6 | 1.397 (3) | C1'—C6' | 1.396 (3) |
C2—C3 | 1.391 (3) | C2'—C3' | 1.389 (3) |
C3—C4 | 1.390 (4) | C3'—C4' | 1.388 (4) |
C3—H3 | 0.98 (3) | C3'—H3' | 0.93 (3) |
C4—C5 | 1.396 (3) | C4'—C5' | 1.396 (3) |
C4—H4 | 0.94 (4) | C4'—H4' | 0.94 (3) |
C5—C6 | 1.398 (3) | C5'—C6' | 1.392 (3) |
C5—C7 | 1.508 (3) | C5'—C7' | 1.507 (3) |
C6—H6 | 0.98 (3) | C6'—H6' | 0.97 (3) |
C7—H7A | 0.9800 | C7'—H7X | 0.9800 |
C7—H7B | 0.9800 | C7'—H7Y | 0.9800 |
C7—H7C | 0.9800 | C7'—H7Z | 0.9800 |
| | | |
C1—O1—H1 | 113 (2) | C1'—O1'—H1' | 112 (2) |
O1—C1—C2 | 124.2 (2) | O1'—C1'—C2' | 124.1 (2) |
O1—C1—C6 | 116.7 (2) | O1'—C1'—C6' | 116.8 (2) |
C2—C1—C6 | 119.1 (2) | C2'—C1'—C6' | 119.1 (2) |
C1—C2—C3 | 120.7 (2) | C1'—C2'—C3' | 120.7 (2) |
C1—C2—Cl1 | 119.31 (18) | C1'—C2'—Cl1' | 119.26 (18) |
C3—C2—Cl1 | 119.97 (19) | C3'—C2'—Cl1' | 120.01 (18) |
C2—C3—C4 | 119.7 (2) | C2'—C3'—C4' | 119.6 (2) |
C2—C3—H3 | 119.0 (18) | C2'—C3'—H3' | 119.6 (19) |
C4—C3—H3 | 121.3 (18) | C4'—C3'—H3' | 120.7 (19) |
C3—C4—C5 | 120.9 (2) | C3'—C4'—C5' | 120.8 (2) |
C3—C4—H4 | 117 (2) | C3'—C4'—H4' | 121.4 (19) |
C5—C4—H4 | 122 (2) | C5'—C4'—H4' | 117.8 (19) |
C4—C5—C6 | 118.5 (2) | C6'—C5'—C4' | 118.7 (2) |
C4—C5—C7 | 121.5 (2) | C6'—C5'—C7' | 120.2 (2) |
C6—C5—C7 | 119.9 (2) | C4'—C5'—C7' | 121.2 (2) |
C1—C6—C5 | 121.2 (2) | C5'—C6'—C1' | 121.1 (2) |
C1—C6—H6 | 119.1 (18) | C5'—C6'—H6' | 118.4 (16) |
C5—C6—H6 | 119.8 (18) | C1'—C6'—H6' | 120.5 (16) |
C5—C7—H7A | 109.5 | C5'—C7'—H7X | 109.5 |
C5—C7—H7B | 109.5 | C5'—C7'—H7Y | 109.5 |
H7A—C7—H7B | 109.5 | H7X—C7'—H7Y | 109.5 |
C5—C7—H7C | 109.5 | C5'—C7'—H7Z | 109.5 |
H7A—C7—H7C | 109.5 | H7X—C7'—H7Z | 109.5 |
H7B—C7—H7C | 109.5 | H7Y—C7'—H7Z | 109.5 |
| | | |
O1—C1—C2—C3 | 179.3 (2) | O1'—C1'—C2'—C3' | 179.3 (2) |
C6—C1—C2—C3 | 0.7 (3) | C6'—C1'—C2'—C3' | −1.0 (3) |
O1—C1—C2—Cl1 | 0.0 (3) | O1'—C1'—C2'—Cl1' | −0.5 (3) |
C6—C1—C2—Cl1 | −178.57 (16) | C6'—C1'—C2'—Cl1' | 179.16 (17) |
C1—C2—C3—C4 | −0.4 (4) | C1'—C2'—C3'—C4' | 0.3 (4) |
Cl1—C2—C3—C4 | 178.87 (18) | Cl1'—C2'—C3'—C4' | −179.81 (18) |
C2—C3—C4—C5 | −0.4 (4) | C2'—C3'—C4'—C5' | 0.6 (4) |
C3—C4—C5—C6 | 0.7 (3) | C3'—C4'—C5'—C6' | −0.9 (3) |
C3—C4—C5—C7 | −179.7 (2) | C3'—C4'—C5'—C7' | 178.6 (2) |
O1—C1—C6—C5 | −178.96 (19) | C4'—C5'—C6'—C1' | 0.2 (3) |
C2—C1—C6—C5 | −0.3 (3) | C7'—C5'—C6'—C1' | −179.2 (2) |
C4—C5—C6—C1 | −0.4 (3) | O1'—C1'—C6'—C5' | −179.6 (2) |
C7—C5—C6—C1 | −180.0 (2) | C2'—C1'—C6'—C5' | 0.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cl1 | 0.88 (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···Cl1i | 0.98 (3) | 2.86 (3) | 3.830 (3) | 169 (2) |
C6′—H6′···Cl1′i | 0.97 (3) | 2.83 (3) | 3.784 (3) | 170 (2) |
O1—H1···O1′ii | 0.88 (2) | 1.99 (2) | 2.798 (2) | 152 (3) |
O1′—H1′···O1 | 0.81 (3) | 2.09 (3) | 2.843 (3) | 155 (3) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
(II) 4-chloro-3-methylphenol
top
Crystal data top
C7H7ClO | F(000) = 592 |
Mr = 142.58 | Dx = 1.422 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6998 (4) Å | Cell parameters from 36420 reflections |
b = 14.2926 (5) Å | θ = 2.9–27.5° |
c = 8.7105 (3) Å | µ = 0.48 mm−1 |
β = 91.152 (2)° | T = 120 K |
V = 1331.81 (8) Å3 | Block, colourless |
Z = 8 | 0.18 × 0.14 × 0.10 mm |
Data collection top
Enraf Nonius KappaCCD area detector diffractometer | 3003 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 2032 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
ϕ and ω scans to fill Ewald sphere | h = −13→13 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | k = −18→18 |
Tmin = 0.982, Tmax = 1.000 | l = −11→11 |
15691 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H 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 parameters | Δρmax = 0.34 e Å−3 |
2 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
C7H7ClO | V = 1331.81 (8) Å3 |
Mr = 142.58 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.6998 (4) Å | µ = 0.48 mm−1 |
b = 14.2926 (5) Å | T = 120 K |
c = 8.7105 (3) Å | 0.18 × 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 = 1.000 | Rint = 0.068 |
15691 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 2 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.34 e Å−3 |
3003 reflections | Δρmin = −0.35 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Cl1 | 0.73208 (5) | 0.12767 (4) | 0.46204 (6) | 0.03134 (19) | |
O1 | 0.19307 (13) | 0.18011 (10) | 0.53937 (16) | 0.0232 (4) | |
H1 | 0.170 (3) | 0.2119 (19) | 0.620 (3) | 0.068 (10)* | |
C1 | 0.32058 (19) | 0.16947 (15) | 0.5274 (2) | 0.0202 (5) | |
C2 | 0.3617 (2) | 0.11236 (15) | 0.4106 (2) | 0.0206 (5) | |
H2 | 0.299 (2) | 0.0829 (15) | 0.345 (3) | 0.022 (6)* | |
C3 | 0.4885 (2) | 0.09894 (14) | 0.3857 (2) | 0.0211 (5) | |
C4 | 0.57215 (19) | 0.14412 (15) | 0.4861 (2) | 0.0227 (5) | |
C5 | 0.5316 (2) | 0.20121 (15) | 0.6030 (3) | 0.0254 (5) | |
H5 | 0.593 (2) | 0.2317 (16) | 0.674 (3) | 0.031 (6)* | |
C6 | 0.4051 (2) | 0.21434 (15) | 0.6239 (2) | 0.0238 (5) | |
H6 | 0.379 (2) | 0.2513 (17) | 0.706 (3) | 0.030 (6)* | |
C7 | 0.5318 (2) | 0.03937 (16) | 0.2558 (2) | 0.0256 (5) | |
H7A | 0.4593 | 0.0179 | 0.1949 | 0.050 (8)* | |
H7B | 0.5774 | −0.0149 | 0.2969 | 0.039 (7)* | |
H7C | 0.5870 | 0.0760 | 0.1906 | 0.039 (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) | |
H7X | 0.7784 | 0.0632 | −0.1825 | 0.056 (8)* | |
H7Y | 0.7904 | 0.1732 | −0.1511 | 0.043 (7)* | |
H7Z | 0.6804 | 0.1146 | −0.0746 | 0.048 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0204 (3) | 0.0362 (4) | 0.0374 (3) | −0.0008 (2) | 0.0029 (2) | −0.0024 (3) |
O1 | 0.0219 (8) | 0.0268 (9) | 0.0210 (8) | 0.0022 (7) | 0.0027 (7) | −0.0020 (7) |
C1 | 0.0215 (11) | 0.0192 (11) | 0.0198 (10) | 0.0015 (9) | 0.0013 (9) | 0.0054 (9) |
C2 | 0.0223 (11) | 0.0203 (12) | 0.0192 (11) | −0.0016 (9) | −0.0027 (10) | 0.0025 (9) |
C3 | 0.0240 (11) | 0.0185 (12) | 0.0209 (11) | 0.0013 (9) | 0.0020 (9) | 0.0040 (9) |
C4 | 0.0202 (11) | 0.0237 (12) | 0.0243 (11) | −0.0002 (9) | 0.0018 (9) | 0.0030 (9) |
C5 | 0.0269 (12) | 0.0231 (13) | 0.0262 (12) | −0.0030 (10) | −0.0014 (10) | −0.0021 (10) |
C6 | 0.0282 (12) | 0.0223 (12) | 0.0210 (11) | 0.0022 (10) | 0.0019 (10) | −0.0033 (9) |
C7 | 0.0245 (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—C4 | 1.744 (2) | Cl1'—C4' | 1.751 (2) |
O1—C1 | 1.379 (2) | O1'—C1' | 1.386 (2) |
O1—H1 | 0.877 (17) | O1'—H1' | 0.870 (17) |
C1—C6 | 1.380 (3) | C1'—C2' | 1.379 (3) |
C1—C2 | 1.383 (3) | C1'—C6' | 1.381 (3) |
C2—C3 | 1.392 (3) | C2'—C3' | 1.391 (3) |
C2—H2 | 0.97 (2) | C2'—H2' | 0.94 (2) |
C3—C4 | 1.397 (3) | C3'—C4' | 1.392 (3) |
C3—C7 | 1.497 (3) | C3'—C7' | 1.505 (3) |
C4—C5 | 1.382 (3) | C4'—C5' | 1.380 (3) |
C5—C6 | 1.383 (3) | C5'—C6' | 1.385 (3) |
C5—H5 | 0.99 (2) | C5'—H5' | 0.91 (2) |
C6—H6 | 0.94 (2) | C6'—H6' | 0.93 (3) |
C7—H7A | 0.9800 | C7'—H7X | 0.9800 |
C7—H7B | 0.9800 | C7'—H7Y | 0.9800 |
C7—H7C | 0.9800 | C7'—H7Z | 0.9800 |
| | | |
C1—O1—H1 | 114 (2) | C1'—O1'—H1' | 112.8 (19) |
O1—C1—C2 | 116.79 (18) | C2'—C1'—C6' | 120.9 (2) |
O1—C1—C6 | 122.64 (18) | C2'—C1'—O1' | 116.87 (19) |
C6—C1—C2 | 120.6 (2) | C6'—C1'—O1' | 122.19 (19) |
C1—C2—C3 | 121.4 (2) | C1'—C2'—C3' | 121.2 (2) |
C1—C2—H2 | 117.9 (12) | C1'—C2'—H2' | 119.2 (14) |
C3—C2—H2 | 120.6 (12) | C3'—C2'—H2' | 119.7 (14) |
C2—C3—C4 | 116.92 (19) | C2'—C3'—C4' | 117.1 (2) |
C2—C3—C7 | 120.9 (2) | C2'—C3'—C7' | 120.2 (2) |
C4—C3—C7 | 122.15 (19) | C4'—C3'—C7' | 122.8 (2) |
C5—C4—C3 | 121.9 (2) | C5'—C4'—C3' | 122.0 (2) |
C5—C4—Cl1 | 119.43 (17) | C5'—C4'—Cl1' | 118.44 (18) |
C3—C4—Cl1 | 118.70 (16) | C3'—C4'—Cl1' | 119.54 (17) |
C4—C5—C6 | 120.0 (2) | C4'—C5'—C6' | 120.0 (2) |
C4—C5—H5 | 120.4 (13) | C4'—C5'—H5' | 118.4 (15) |
C6—C5—H5 | 119.5 (13) | C6'—C5'—H5' | 121.6 (15) |
C1—C6—C5 | 119.2 (2) | C1'—C6'—C5' | 118.8 (2) |
C1—C6—H6 | 121.4 (14) | C1'—C6'—H6' | 120.6 (15) |
C5—C6—H6 | 119.3 (14) | C5'—C6'—H6' | 120.5 (15) |
C3—C7—H7A | 109.5 | C3'—C7'—H7X | 109.5 |
C3—C7—H7B | 109.5 | C3'—C7'—H7Y | 109.5 |
H7A—C7—H7B | 109.5 | H7X—C7'—H7Y | 109.5 |
C3—C7—H7C | 109.5 | C3'—C7'—H7Z | 109.5 |
H7A—C7—H7C | 109.5 | H7X—C7'—H7Z | 109.5 |
H7B—C7—H7C | 109.5 | H7Y—C7'—H7Z | 109.5 |
| | | |
O1—C1—C2—C3 | 178.17 (18) | C6'—C1'—C2'—C3' | −0.6 (3) |
C6—C1—C2—C3 | −0.6 (3) | O1'—C1'—C2'—C3' | 178.80 (18) |
C1—C2—C3—C4 | 1.4 (3) | C1'—C2'—C3'—C4' | 0.5 (3) |
C1—C2—C3—C7 | −178.04 (19) | C1'—C2'—C3'—C7' | −179.7 (2) |
C2—C3—C4—C5 | −1.4 (3) | C2'—C3'—C4'—C5' | −0.5 (3) |
C7—C3—C4—C5 | 178.08 (19) | C7'—C3'—C4'—C5' | 179.7 (2) |
C2—C3—C4—Cl1 | 178.73 (15) | C2'—C3'—C4'—Cl1' | 179.41 (15) |
C7—C3—C4—Cl1 | −1.8 (3) | C7'—C3'—C4'—Cl1' | −0.5 (3) |
C3—C4—C5—C6 | 0.5 (3) | C3'—C4'—C5'—C6' | 0.6 (3) |
Cl1—C4—C5—C6 | −179.58 (17) | Cl1'—C4'—C5'—C6' | −179.30 (15) |
O1—C1—C6—C5 | −179.01 (19) | C2'—C1'—C6'—C5' | 0.7 (3) |
C2—C1—C6—C5 | −0.3 (3) | O1'—C1'—C6'—C5' | −178.68 (17) |
C4—C5—C6—C1 | 0.3 (3) | C4'—C5'—C6'—C1' | −0.6 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1′i | 0.88 (2) | 1.85 (2) | 2.711 (2) | 165 (3) |
O1′—H1′···O1ii | 0.87 (2) | 1.85 (2) | 2.714 (2) | 175 (3) |
Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C7H7ClO | C7H7ClO |
Mr | 142.58 | 142.58 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 120 | 120 |
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) |
V (Å3) | 1312.7 (5) | 1331.81 (8) |
Z | 8 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.49 | 0.48 |
Crystal size (mm) | 0.40 × 0.32 × 0.26 | 0.18 × 0.14 × 0.10 |
|
Data collection |
Diffractometer | Enraf Nonius KappaCCD area detector diffractometer | Enraf Nonius KappaCCD area detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.560, 0.882 | 0.982, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11902, 2998, 2571 | 15691, 3003, 2032 |
Rint | 0.088 | 0.068 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.138, 1.10 | 0.046, 0.113, 1.03 |
No. of reflections | 2998 | 3003 |
No. of parameters | 204 | 203 |
No. of restraints | 1 | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.81, −0.44 | 0.34, −0.35 |
Selected geometric parameters (Å, º) for (I) topCl1—C2 | 1.746 (2) | Cl1'—C2' | 1.743 (2) |
O1—C1 | 1.373 (3) | O1'—C1' | 1.375 (3) |
C5—C7 | 1.508 (3) | C5'—C7' | 1.507 (3) |
| | | |
O1—C1—C2 | 124.2 (2) | O1'—C1'—C2' | 124.1 (2) |
O1—C1—C6 | 116.7 (2) | O1'—C1'—C6' | 116.8 (2) |
C1—C2—Cl1 | 119.31 (18) | C1'—C2'—Cl1' | 119.26 (18) |
| | | |
O1—C1—C2—Cl1 | 0.0 (3) | O1'—C1'—C2'—Cl1' | −0.5 (3) |
C6—C1—C2—Cl1 | −178.57 (16) | C6'—C1'—C2'—Cl1' | 179.16 (17) |
Cl1—C2—C3—C4 | 178.87 (18) | Cl1'—C2'—C3'—C4' | −179.81 (18) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cl1 | 0.88 (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···Cl1i | 0.98 (3) | 2.86 (3) | 3.830 (3) | 169 (2) |
C6'—H6'···Cl1'i | 0.97 (3) | 2.83 (3) | 3.784 (3) | 170 (2) |
O1—H1···O1'ii | 0.88 (2) | 1.99 (2) | 2.798 (2) | 152 (3) |
O1'—H1'···O1 | 0.81 (3) | 2.09 (3) | 2.843 (3) | 155 (3) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2. |
C—H···π interactions (Å, °) for 2-chloro-5-methylphenol topC—H | Cg(I) | symmetry | H···Cg(I) | C—H···Cg(I) | C···Cg(I) |
C4—H4 | 1 | -x,-y,1 − z | 3.37 (4) | 87 (2) | 3.453 (3) |
C7—H7B | 1 | x,0.5 − y,0.5 + z | 2.73 | 166 | 3.692 (3) |
C7'—H7X | 2 | x,0.5 − y,0.5 + z | 3.09 | 112 | 3.579 (3) |
C7'—H7Z | 2 | x,0.5 − y,0.5 + z | 3.15 | 108 | 3.579 (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 topCg(I) | Cg(J) | symmetry | Cg···Cg | dihedral_angle | interplanar | offset |
1 | 1 | -x,-y,1 − z | 3.941 (2) | 0.0 | 3.387 (2) | 2.02 |
2 | 2 | 1 − x,-y,2 − z | 3.904 (2) | 0.0 | 3.461 (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) topCl1—C4 | 1.744 (2) | Cl1'—C4' | 1.751 (2) |
O1—C1 | 1.379 (2) | O1'—C1' | 1.386 (2) |
C3—C7 | 1.497 (3) | C3'—C7' | 1.505 (3) |
| | | |
O1—C1—C2 | 116.79 (18) | C2'—C1'—O1' | 116.87 (19) |
O1—C1—C6 | 122.64 (18) | C6'—C1'—O1' | 122.19 (19) |
C5—C4—Cl1 | 119.43 (17) | C5'—C4'—Cl1' | 118.44 (18) |
| | | |
C1—C2—C3—C7 | −178.04 (19) | C1'—C2'—C3'—C7' | −179.7 (2) |
C7—C3—C4—Cl1 | −1.8 (3) | C7'—C3'—C4'—Cl1' | −0.5 (3) |
Cl1—C4—C5—C6 | −179.58 (17) | Cl1'—C4'—C5'—C6' | −179.30 (15) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O1'i | 0.877 (17) | 1.854 (19) | 2.711 (2) | 165 (3) |
O1'—H1'···O1ii | 0.870 (17) | 1.846 (18) | 2.714 (2) | 175 (3) |
Symmetry codes: (i) x−1, −y+1/2, z+1/2; (ii) x+1, y, z. |
C—H···π interactions (Å, °) for 4-chloro-3-methylphenol topC—H | Cg(I) | symmetry | H···Cg(I) | C—H···Cg(I) | C···Cg(I) |
C6—H6 | 1 | x,0.5 − y,0.5 + z | 3.00 (3) | 147 (2) | 3.823 (3) |
C7—H7B | 1 | 1 − x,-y,1 − z | 2.67 | 141 | 3.492 (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 topCg(I) | Cg(J) | symmetry | Cg···Cg | dihedral_angle | interplanar | offset |
2 | 2 | 2 − x,-y,-z | 3.885 (2) | 0.0 | 3.500 (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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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).