Variable-temperature studies of the 4-isopropylphenol crystal structure from X-ray diffraction. Comparison of thermal expansion and molecular dynamics with spectroscopic results

Crystalline 4-isopropylphenol, C₉H₁₂O, an optically non-linear material, was studied by X-ray diffraction in order to deter­mine its structure at several temperatures in the 95-300 K range. The thermal expansion coefficients have been calculated from the lattice parameters' dependence on temperature. The rigid-body analysis of the anisotropic displacement parameters including the correlation with the internal motion of large amplitude provided the values of the molecular translation and libration tensors at the temperatures studied and was used to characterize the torsional motion of the isopropyl group. The calculated normal modes and internal torsion frequency were compared with the wave numbers at the maximum of bands in the low-frequency Raman scattering, FTIR and inelastic neutron scattering spectra.

Computing details

For all compounds, data collection: Kuma KM4CCD Software, 1999; cell refinement: Kuma KM4CCD Software, 1999; data reduction: Kuma KM4CCD Software, 1999; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997b).

Figures

(ipp95dc) '4-Isopropyl-phenol'

Crystal data

C9H12O	Dx = 1.140 Mg m^−3
Mr = 136.19	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41	Cell parameters from 887 reflections
a = 9.848 (3) Å	µ = 0.07 mm^−1
c = 8.166 (2) Å	T = 95 K
V = 793.3 (4) Å^3	Prism, colourless
Z = 4	0.72 × 0.44 × 0.29 mm
F(000) = 296

Data collection

Kuma Diffraction KM4CCD diffractometer	2018 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.064
Graphite monochromator	θmax = 31.2°, θmin = 3.8°
ω scans	h = −13→11
5936 measured reflections	k = −14→14
2162 independent reflections	l = −11→10

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)] = 0.060	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.150	Calculated w = 1/[σ^2(Fo^2) + (0.0686P)^2 + 0.4966P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
2162 reflections	Δρmax = 0.29 e Å^−3
92 parameters	Δρmin = −0.45 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 2.1 (18)

Special details

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
O1	0.13173 (13)	0.98851 (13)	0.13042 (19)	0.0180 (3)
H1	0.0927	0.9541	0.0490	0.027*
C1	0.26012 (16)	0.93315 (17)	0.1462 (2)	0.0143 (3)
C2	0.34146 (18)	0.98130 (17)	0.2727 (2)	0.0169 (3)
H2	0.3091	1.0511	0.3428	0.020*
C3	0.47024 (17)	0.92696 (18)	0.2962 (3)	0.0180 (3)
H3	0.5248	0.9594	0.3838	0.022*
C4	0.52115 (18)	0.82520 (18)	0.1932 (2)	0.0162 (3)
C5	0.43876 (18)	0.78005 (18)	0.0664 (2)	0.0164 (3)
H5	0.4715	0.7115	−0.0051	0.020*
C6	0.30853 (18)	0.83324 (17)	0.0413 (2)	0.0161 (3)
H6	0.2539	0.8014	−0.0465	0.019*
C7	0.66042 (19)	0.7643 (2)	0.2225 (3)	0.0206 (4)
H7	0.6838	0.7070	0.1255	0.025*
C8	0.6596 (2)	0.6730 (3)	0.3736 (3)	0.0334 (5)
H8A	0.7502	0.6342	0.3897	0.050*
H8B	0.5936	0.5998	0.3581	0.050*
H8C	0.6344	0.7265	0.4701	0.050*
C9	0.7698 (2)	0.8749 (2)	0.2386 (3)	0.0298 (5)
H9A	0.8584	0.8324	0.2570	0.045*
H9B	0.7477	0.9341	0.3312	0.045*
H9C	0.7728	0.9286	0.1377	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0144 (6)	0.0188 (6)	0.0209 (7)	0.0019 (4)	−0.0022 (5)	−0.0053 (5)
C1	0.0122 (7)	0.0143 (7)	0.0163 (8)	0.0001 (5)	0.0008 (6)	−0.0003 (6)
C2	0.0162 (7)	0.0160 (7)	0.0186 (9)	0.0010 (6)	−0.0015 (6)	−0.0047 (6)
C3	0.0156 (7)	0.0187 (8)	0.0196 (9)	0.0007 (6)	−0.0022 (7)	−0.0055 (7)
C4	0.0151 (7)	0.0175 (7)	0.0159 (8)	0.0003 (6)	0.0008 (6)	−0.0020 (6)
C5	0.0161 (7)	0.0175 (7)	0.0157 (8)	0.0007 (5)	0.0000 (6)	−0.0038 (6)
C6	0.0162 (7)	0.0166 (7)	0.0156 (8)	−0.0011 (5)	−0.0013 (6)	−0.0028 (6)
C7	0.0162 (8)	0.0249 (9)	0.0208 (10)	0.0045 (6)	−0.0019 (7)	−0.0058 (7)
C8	0.0331 (11)	0.0397 (12)	0.0274 (12)	0.0151 (9)	−0.0029 (10)	0.0052 (10)
C9	0.0151 (8)	0.0389 (12)	0.0353 (12)	−0.0006 (7)	−0.0015 (8)	−0.0141 (10)

Geometric parameters (Å, º)

O1—C1	1.383 (2)	C4—C5	1.389 (3)
C1—C6	1.390 (2)	C4—C7	1.516 (2)
C1—C2	1.391 (2)	C5—C6	1.401 (2)
C2—C3	1.390 (2)	C7—C8	1.528 (3)
C3—C4	1.402 (3)	C7—C9	1.538 (3)
O1—C1—C6	122.39 (16)	C3—C4—C7	120.82 (16)
O1—C1—C2	117.45 (15)	C4—C5—C6	121.57 (16)
C6—C1—C2	120.15 (15)	C1—C6—C5	119.31 (16)
C3—C2—C1	119.76 (16)	C4—C7—C8	110.84 (17)
C2—C3—C4	121.28 (17)	C4—C7—C9	111.46 (16)
C5—C4—C3	117.91 (16)	C8—C7—C9	110.66 (19)
C5—C4—C7	121.26 (16)
O1—C1—C2—C3	178.58 (17)	O1—C1—C6—C5	−178.87 (16)
C6—C1—C2—C3	−1.5 (3)	C2—C1—C6—C5	1.2 (3)
C1—C2—C3—C4	0.9 (3)	C4—C5—C6—C1	−0.3 (3)
C2—C3—C4—C5	0.0 (3)	C5—C4—C7—C8	−106.4 (2)
C2—C3—C4—C7	−178.53 (18)	C3—C4—C7—C8	72.1 (2)
C3—C4—C5—C6	−0.3 (3)	C5—C4—C7—C9	129.9 (2)
C7—C4—C5—C6	178.23 (18)	C3—C4—C7—C9	−51.7 (3)

(4ip180) '4-Isopropyl-phenol'

Crystal data

C9H12O	Dx = 1.131 Mg m^−3
Mr = 136.19	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41	Cell parameters from 1091 reflections
a = 9.859 (2) Å	µ = 0.07 mm^−1
c = 8.221 (1) Å	T = 180 K
V = 799.6 (2) Å^3	Prism, colourless
Z = 4	1.02 × 0.51 × 0.36 mm
F(000) = 296

Data collection

Kuma Diffraction KM4CCD diffractometer	1281 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.042
Graphite monochromator	θmax = 31.3°, θmin = 3.2°
ω scans	h = −14→14
4181 measured reflections	k = −13→14
1453 independent reflections	l = −12→7

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.059	Calculated w = 1/[σ^2(Fo^2) + (0.0956P)^2 + 0.1106P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.168	(Δ/σ)max < 0.001
S = 1.20	Δρmax = 0.34 e Å^−3
1453 reflections	Δρmin = −0.40 e Å^−3
93 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.32 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0 (2)

Special details

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
O1	0.98848 (16)	0.86720 (16)	0.1941 (2)	0.0319 (4)
H1	0.9519	0.9067	0.1180	0.048*
C1	0.9332 (2)	0.7397 (2)	0.2102 (3)	0.0257 (4)
C2	0.9812 (2)	0.6588 (2)	0.3354 (3)	0.0299 (5)
H2	1.0496	0.6904	0.4034	0.036*
C3	0.9271 (2)	0.5306 (2)	0.3592 (3)	0.0317 (5)
H3	0.9588	0.4779	0.4449	0.038*
C4	0.8262 (2)	0.4790 (2)	0.2577 (3)	0.0282 (4)
C5	0.7810 (2)	0.5611 (2)	0.1318 (3)	0.0293 (4)
H5	0.7142	0.5289	0.0620	0.035*
C6	0.8335 (2)	0.6909 (2)	0.1073 (3)	0.0277 (4)
H6	0.8016	0.7443	0.0223	0.033*
C7	0.7662 (3)	0.3407 (2)	0.2866 (3)	0.0353 (5)
H7	0.7099	0.3181	0.1922	0.042*
C8	0.6747 (4)	0.3401 (4)	0.4365 (5)	0.0608 (10)
H8A	0.6371	0.2512	0.4513	0.091*
H8B	0.6026	0.4044	0.4219	0.091*
H8C	0.7269	0.3645	0.5307	0.091*
C9	0.8769 (4)	0.2316 (3)	0.3009 (5)	0.0513 (8)
H9A	0.8354	0.1449	0.3187	0.077*
H9B	0.9354	0.2528	0.3906	0.077*
H9C	0.9289	0.2291	0.2022	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0350 (8)	0.0277 (8)	0.0331 (9)	−0.0026 (6)	−0.0078 (7)	0.0036 (6)
C1	0.0263 (9)	0.0237 (9)	0.0270 (9)	0.0018 (6)	−0.0015 (7)	−0.0008 (7)
C2	0.0289 (10)	0.0319 (10)	0.0288 (10)	−0.0022 (7)	−0.0088 (8)	0.0015 (8)
C3	0.0358 (11)	0.0298 (9)	0.0293 (10)	−0.0007 (7)	−0.0099 (8)	0.0042 (8)
C4	0.0309 (10)	0.0274 (9)	0.0263 (10)	−0.0018 (7)	−0.0031 (8)	0.0006 (7)
C5	0.0297 (9)	0.0319 (10)	0.0262 (10)	−0.0012 (7)	−0.0060 (8)	−0.0005 (8)
C6	0.0290 (9)	0.0303 (10)	0.0238 (9)	0.0007 (7)	−0.0043 (7)	0.0021 (7)
C7	0.0440 (12)	0.0281 (10)	0.0338 (12)	−0.0072 (8)	−0.0107 (10)	0.0034 (8)
C8	0.075 (2)	0.0587 (19)	0.0485 (19)	−0.0286 (17)	0.0107 (16)	0.0022 (16)
C9	0.0654 (18)	0.0296 (11)	0.0590 (18)	−0.0010 (11)	−0.0229 (15)	0.0012 (12)

Geometric parameters (Å, º)

O1—C1	1.377 (2)	C4—C5	1.388 (3)
C1—C6	1.383 (3)	C4—C7	1.505 (3)
C1—C2	1.386 (3)	C5—C6	1.395 (3)
C2—C3	1.386 (3)	C7—C8	1.528 (5)
C3—C4	1.395 (3)	C7—C9	1.537 (4)
O1—C1—C6	122.68 (19)	C3—C4—C7	121.1 (2)
O1—C1—C2	117.56 (18)	C4—C5—C6	121.64 (19)
C6—C1—C2	119.76 (18)	C1—C6—C5	119.63 (19)
C1—C2—C3	119.94 (18)	C4—C7—C8	111.3 (2)
C2—C3—C4	121.5 (2)	C4—C7—C9	111.6 (2)
C5—C4—C3	117.47 (19)	C8—C7—C9	110.8 (3)
C5—C4—C7	121.39 (19)
O1—C1—C2—C3	178.7 (2)	O1—C1—C6—C5	−179.3 (2)
C6—C1—C2—C3	−1.4 (3)	C2—C1—C6—C5	0.7 (3)
C1—C2—C3—C4	1.2 (4)	C4—C5—C6—C1	0.2 (3)
C2—C3—C4—C5	−0.4 (4)	C5—C4—C7—C8	−106.5 (3)
C2—C3—C4—C7	−178.8 (2)	C3—C4—C7—C8	71.9 (3)
C3—C4—C5—C6	−0.3 (3)	C5—C4—C7—C9	129.2 (3)
C7—C4—C5—C6	178.1 (2)	C3—C4—C7—C9	−52.4 (3)

(4ip300) '4-Isopropyl-phenol'

Crystal data

C9H12O	F(000) = 296
Mr = 136.19	Dx = 1.103 Mg m^−3
Tetragonal, P41	Mo Kα radiation, λ = 0.71073 Å
a = 9.928 (1) Å	µ = 0.07 mm^−1
c = 8.316 (1) Å	T = 293 K
V = 820.16 (15) Å^3	Prism, colourless
Z = 4	1.02 × 0.51 × 0.36 mm

Data collection

Radiation source: fine-focus sealed tube	Rint = 0.045
Graphite monochromator	θmax = 31.3°, θmin = 3.8°
ω scans	h = −14→14
4448 measured reflections	k = −14→14
1519 independent reflections	l = −12→8
1049 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.060	Calculated w = 1/[σ^2(Fo^2) + (0.105P)^2 + 0.0244P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.184	(Δ/σ)max = 0.001
S = 1.10	Δρmax = 0.22 e Å^−3
1519 reflections	Δρmin = −0.19 e Å^−3
90 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.34 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: 2 (2)

Special details

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
O1	0.86515 (18)	0.01214 (18)	0.0786 (2)	0.0575 (5)
H1	0.9021	0.0447	−0.0005	0.086*
C1	0.7387 (2)	0.0668 (2)	0.0953 (3)	0.0478 (5)
C2	0.6590 (3)	0.0192 (3)	0.2194 (3)	0.0557 (6)
H2	0.6908	−0.0487	0.2864	0.067*
C3	0.5325 (3)	0.0726 (3)	0.2436 (3)	0.0586 (7)
H3	0.4807	0.0415	0.3290	0.070*
C4	0.4805 (3)	0.1717 (3)	0.1435 (3)	0.0533 (6)
C5	0.5615 (3)	0.2172 (3)	0.0196 (3)	0.0546 (6)
H5	0.5293	0.2839	−0.0489	0.066*
C6	0.6898 (3)	0.1657 (2)	−0.0047 (3)	0.0518 (6)
H6	0.7427	0.1980	−0.0885	0.062*
C7	0.3422 (3)	0.2295 (3)	0.1716 (4)	0.0668 (8)
H7	0.3203	0.2869	0.0795	0.080*
C8	0.3406 (3)	0.3181 (4)	0.3223 (5)	0.1138 (17)
H8A	0.2519	0.3543	0.3377	0.171*
H8B	0.4038	0.3905	0.3096	0.171*
H8C	0.3652	0.2650	0.4143	0.171*
C9	0.2355 (3)	0.1205 (4)	0.1817 (5)	0.0939 (12)
H9A	0.1489	0.1611	0.1990	0.141*
H9B	0.2559	0.0611	0.2695	0.141*
H9C	0.2341	0.0703	0.0831	0.141*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0513 (10)	0.0594 (10)	0.0619 (11)	0.0041 (7)	0.0054 (8)	0.0110 (8)
C1	0.0499 (12)	0.0472 (11)	0.0462 (11)	−0.0018 (9)	−0.0008 (9)	0.0011 (9)
C2	0.0562 (13)	0.0546 (13)	0.0564 (13)	0.0018 (10)	0.0014 (11)	0.0138 (11)
C3	0.0563 (13)	0.0664 (16)	0.0533 (13)	0.0009 (11)	0.0079 (11)	0.0169 (12)
C4	0.0516 (12)	0.0564 (13)	0.0519 (13)	0.0033 (10)	0.0002 (10)	0.0050 (11)
C5	0.0575 (14)	0.0562 (13)	0.0501 (12)	0.0020 (10)	−0.0016 (10)	0.0123 (10)
C6	0.0548 (13)	0.0550 (13)	0.0455 (11)	−0.0027 (9)	0.0039 (10)	0.0081 (10)
C7	0.0576 (14)	0.0823 (19)	0.0603 (15)	0.0151 (13)	0.0055 (12)	0.0165 (14)
C8	0.108 (3)	0.135 (4)	0.098 (3)	0.050 (3)	0.004 (3)	−0.024 (3)
C9	0.0555 (17)	0.122 (3)	0.104 (3)	0.0084 (19)	0.0066 (18)	0.037 (2)

Geometric parameters (Å, º)

O1—C1	1.375 (3)	C4—C5	1.383 (4)
C1—C6	1.375 (3)	C4—C7	1.506 (4)
C1—C2	1.384 (3)	C5—C6	1.387 (4)
C2—C3	1.378 (4)	C7—C9	1.517 (5)
C3—C4	1.388 (3)	C7—C8	1.532 (5)
O1—C1—C6	122.9 (2)	C3—C4—C7	121.1 (2)
O1—C1—C2	117.5 (2)	C4—C5—C6	121.4 (2)
C6—C1—C2	119.5 (2)	C1—C6—C5	120.0 (2)
C3—C2—C1	119.9 (2)	C4—C7—C9	111.9 (3)
C2—C3—C4	121.6 (2)	C4—C7—C8	110.8 (3)
C5—C4—C3	117.5 (2)	C9—C7—C8	111.0 (3)
C5—C4—C7	121.4 (2)
O1—C1—C2—C3	178.6 (3)	O1—C1—C6—C5	−179.5 (2)
C6—C1—C2—C3	−1.1 (4)	C2—C1—C6—C5	0.2 (4)
C1—C2—C3—C4	1.6 (5)	C4—C5—C6—C1	0.2 (4)
C2—C3—C4—C5	−1.2 (4)	C5—C4—C7—C9	127.9 (3)
C2—C3—C4—C7	−179.8 (3)	C3—C4—C7—C9	−53.6 (4)
C3—C4—C5—C6	0.3 (4)	C5—C4—C7—C8	−107.7 (3)
C7—C4—C5—C6	178.9 (3)	C3—C4—C7—C8	70.9 (4)