Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010403015X/ga1076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010403015X/ga1076Isup2.hkl |
CCDC reference: 263062
The sample of o,p-BPA (purity 98%) was obtained from the Institute of Heavy Organic Synthesis (Kedzierzyn-Kozle, Poland). Crystals of (I) suitable for X-ray diffraction were crystallized from ethanol by slow evaporation of the solvent at a constant temperature of 293 K.
All H atoms were refined in geometrically idealized positions, with C—H distances in the range 0.93–0.96 Å and O—H distances of 0.82 Å, with Uiso(H) = 1.5 (for methyl and hydroxyl) or 1.2 times Ueq(C or O).
Data collection: DARCH software; cell refinement: DARCH software; data reduction: DARCH software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97.
C15H16O2 | F(000) = 488 |
Mr = 228.28 | Dx = 1.238 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 20 reflections |
a = 13.621 (3) Å | θ = 8–15° |
b = 12.461 (2) Å | µ = 0.08 mm−1 |
c = 7.232 (1) Å | T = 293 K |
β = 93.62 (3)° | Plate, colourless |
V = 1225.0 (4) Å3 | 0.50 × 0.35 × 0.04 mm |
Z = 4 |
DARCH-1 diffractometer | 1589 reflections with I > 2σ(I) |
Radiation source: BSW x-ray tube | Rint = 0.006 |
Graphite monochromator | θmax = 27.4°, θmin = 1.5° |
ω/2θ scans | h = −17→17 |
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983) | k = −16→16 |
Tmin = 0.966, Tmax = 0.996 | l = −9→9 |
5620 measured reflections | 3 standard reflections every 100 reflections |
2810 independent reflections | intensity decay: 2.2% |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0401P)2] where P = (Fo2 + 2Fc2)/3 |
2810 reflections | (Δ/σ)max = 0.027 |
158 parameters | Δρmax = 0.08 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
C15H16O2 | V = 1225.0 (4) Å3 |
Mr = 228.28 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.621 (3) Å | µ = 0.08 mm−1 |
b = 12.461 (2) Å | T = 293 K |
c = 7.232 (1) Å | 0.50 × 0.35 × 0.04 mm |
β = 93.62 (3)° |
DARCH-1 diffractometer | 1589 reflections with I > 2σ(I) |
Absorption correction: part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983) | Rint = 0.006 |
Tmin = 0.966, Tmax = 0.996 | 3 standard reflections every 100 reflections |
5620 measured reflections | intensity decay: 2.2% |
2810 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.14 | Δρmax = 0.08 e Å−3 |
2810 reflections | Δρmin = −0.19 e Å−3 |
158 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.41329 (13) | −0.03795 (15) | 0.2452 (2) | 0.0906 (5) | |
H1 | 0.4489 | 0.0258 | 0.2494 | 0.109* | |
C2 | 0.45624 (13) | −0.12856 (14) | 0.1752 (3) | 0.0912 (5) | |
H2 | 0.5193 | −0.1247 | 0.1334 | 0.109* | |
C3 | 0.40668 (13) | −0.22299 (15) | 0.1672 (2) | 0.0961 (5) | |
H3 | 0.4357 | −0.2840 | 0.1206 | 0.115* | |
C4 | 0.31466 (13) | −0.22779 (16) | 0.2277 (3) | 0.0981 (5) | |
H4 | 0.2806 | −0.2925 | 0.2216 | 0.118* | |
C5 | 0.27073 (13) | −0.13841 (14) | 0.2979 (3) | 0.0890 (4) | |
C6 | 0.31862 (13) | −0.03781 (14) | 0.3102 (2) | 0.0897 (4) | |
O7 | 0.17594 (9) | −0.14379 (10) | 0.35549 (19) | 0.0960 (4) | |
H7 | 0.1660 | −0.2038 | 0.3968 | 0.144* | |
C8 | 0.27151 (13) | 0.05871 (14) | 0.3980 (2) | 0.0882 (4) | |
C9 | 0.33327 (14) | 0.16039 (16) | 0.3794 (3) | 0.1017 (5) | |
H9A | 0.3005 | 0.2200 | 0.4326 | 0.153* | |
H9B | 0.3414 | 0.1744 | 0.2507 | 0.153* | |
H9C | 0.3966 | 0.1505 | 0.4432 | 0.153* | |
C10 | 0.26617 (13) | 0.03819 (14) | 0.6043 (2) | 0.0933 (5) | |
H10A | 0.2394 | 0.1002 | 0.6619 | 0.140* | |
H10B | 0.3310 | 0.0241 | 0.6587 | 0.140* | |
H10C | 0.2247 | −0.0227 | 0.6226 | 0.140* | |
C11 | 0.08672 (14) | 0.09981 (15) | 0.3934 (3) | 0.0947 (5) | |
H11 | 0.0906 | 0.0944 | 0.5219 | 0.114* | |
C12 | −0.00174 (14) | 0.12450 (14) | 0.3048 (3) | 0.0959 (5) | |
H12 | −0.0563 | 0.1359 | 0.3735 | 0.115* | |
C13 | −0.01109 (13) | 0.13264 (13) | 0.1157 (3) | 0.0866 (4) | |
C14 | 0.07046 (14) | 0.11704 (15) | 0.0172 (3) | 0.0949 (5) | |
H14 | 0.0661 | 0.1237 | −0.1111 | 0.114* | |
C15 | 0.15901 (13) | 0.09135 (15) | 0.1094 (3) | 0.0925 (5) | |
H15 | 0.2133 | 0.0795 | 0.0404 | 0.111* | |
C16 | 0.17051 (12) | 0.08251 (13) | 0.3007 (2) | 0.0846 (4) | |
O17 | −0.10262 (8) | 0.15825 (11) | 0.03339 (18) | 0.0951 (4) | |
H17 | −0.1037 | 0.1446 | −0.0776 | 0.143* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0813 (9) | 0.0976 (11) | 0.0931 (11) | −0.0075 (8) | 0.0080 (8) | −0.0022 (8) |
C2 | 0.0857 (10) | 0.0958 (11) | 0.0952 (11) | 0.0056 (8) | 0.0062 (8) | −0.0010 (9) |
C3 | 0.0920 (11) | 0.0985 (12) | 0.0964 (11) | 0.0049 (9) | −0.0057 (9) | −0.0184 (9) |
C4 | 0.0896 (10) | 0.0954 (11) | 0.1081 (12) | 0.0042 (9) | −0.0038 (9) | −0.0135 (10) |
C5 | 0.0769 (9) | 0.0997 (11) | 0.0903 (10) | −0.0002 (8) | 0.0047 (8) | −0.0014 (8) |
C6 | 0.0843 (10) | 0.0956 (11) | 0.0886 (10) | −0.0001 (8) | 0.0019 (8) | 0.0004 (8) |
O7 | 0.0874 (7) | 0.0885 (7) | 0.1129 (10) | −0.0064 (5) | 0.0129 (6) | −0.0011 (6) |
C8 | 0.0849 (10) | 0.0865 (10) | 0.0916 (10) | −0.0029 (7) | −0.0059 (8) | 0.0017 (8) |
C9 | 0.0987 (12) | 0.1046 (13) | 0.1004 (13) | −0.0124 (10) | −0.0042 (10) | −0.0001 (10) |
C10 | 0.0922 (11) | 0.0912 (11) | 0.0947 (11) | 0.0004 (8) | −0.0090 (9) | −0.0033 (8) |
C11 | 0.0958 (11) | 0.1038 (12) | 0.0843 (10) | 0.0112 (9) | 0.0052 (9) | 0.0002 (8) |
C12 | 0.0884 (11) | 0.1013 (12) | 0.0988 (12) | 0.0065 (9) | 0.0118 (9) | −0.0014 (9) |
C13 | 0.0818 (9) | 0.0813 (9) | 0.0949 (11) | 0.0067 (7) | −0.0079 (8) | −0.0035 (8) |
C14 | 0.0962 (12) | 0.0982 (12) | 0.0905 (11) | 0.0066 (9) | 0.0068 (9) | 0.0009 (9) |
C15 | 0.0871 (10) | 0.0964 (11) | 0.0947 (11) | 0.0061 (8) | 0.0106 (8) | 0.0008 (9) |
C16 | 0.0879 (10) | 0.0785 (9) | 0.0869 (9) | −0.0012 (7) | 0.0016 (8) | −0.0017 (7) |
O17 | 0.0828 (7) | 0.1016 (8) | 0.0992 (8) | 0.0136 (6) | −0.0076 (6) | −0.0091 (7) |
C1—C2 | 1.382 (2) | C9—H9B | 0.9600 |
C1—C6 | 1.400 (2) | C9—H9C | 0.9600 |
C1—H1 | 0.9300 | C10—H10A | 0.9600 |
C2—C3 | 1.356 (3) | C10—H10B | 0.9600 |
C2—H2 | 0.9300 | C10—H10C | 0.9600 |
C3—C4 | 1.354 (2) | C11—C12 | 1.363 (2) |
C3—H3 | 0.9300 | C11—C16 | 1.377 (2) |
C4—C5 | 1.377 (2) | C11—H11 | 0.9300 |
C4—H4 | 0.9300 | C12—C13 | 1.370 (3) |
C5—O7 | 1.383 (2) | C12—H12 | 0.9300 |
C5—C6 | 1.413 (2) | C13—C14 | 1.371 (2) |
C6—C8 | 1.521 (2) | C13—O17 | 1.384 (2) |
O7—H7 | 0.8200 | C14—C15 | 1.379 (2) |
C8—C10 | 1.520 (2) | C14—H14 | 0.9300 |
C8—C9 | 1.532 (3) | C15—C16 | 1.387 (2) |
C8—C16 | 1.534 (2) | C15—H15 | 0.9300 |
C9—H9A | 0.9600 | O17—H17 | 0.8200 |
C2—C1—C6 | 122.96 (16) | C8—C9—H9C | 109.5 |
C2—C1—H1 | 118.5 | H9A—C9—H9C | 109.5 |
C6—C1—H1 | 118.5 | H9B—C9—H9C | 109.5 |
C3—C2—C1 | 120.22 (17) | C8—C10—H10A | 109.5 |
C3—C2—H2 | 119.9 | C8—C10—H10B | 109.5 |
C1—C2—H2 | 119.9 | H10A—C10—H10B | 109.5 |
C4—C3—C2 | 119.53 (17) | C8—C10—H10C | 109.5 |
C4—C3—H3 | 120.2 | H10A—C10—H10C | 109.5 |
C2—C3—H3 | 120.2 | H10B—C10—H10C | 109.5 |
C3—C4—C5 | 121.07 (18) | C12—C11—C16 | 122.82 (18) |
C3—C4—H4 | 119.5 | C12—C11—H11 | 118.6 |
C5—C4—H4 | 119.5 | C16—C11—H11 | 118.6 |
C4—C5—O7 | 120.51 (16) | C11—C12—C13 | 120.63 (18) |
C4—C5—C6 | 122.09 (17) | C11—C12—H12 | 119.7 |
O7—C5—C6 | 117.39 (15) | C13—C12—H12 | 119.7 |
C1—C6—C5 | 114.14 (15) | C14—C13—C12 | 118.76 (17) |
C1—C6—C8 | 124.27 (16) | C14—C13—O17 | 123.15 (17) |
C5—C6—C8 | 121.50 (16) | C12—C13—O17 | 118.08 (18) |
C5—O7—H7 | 109.5 | C13—C14—C15 | 119.65 (18) |
C10—C8—C6 | 108.93 (14) | C13—C14—H14 | 120.2 |
C10—C8—C9 | 106.63 (15) | C15—C14—H14 | 120.2 |
C6—C8—C9 | 111.65 (15) | C14—C15—C16 | 122.77 (17) |
C10—C8—C16 | 112.69 (15) | C14—C15—H15 | 118.6 |
C6—C8—C16 | 110.56 (14) | C16—C15—H15 | 118.6 |
C9—C8—C16 | 106.34 (14) | C11—C16—C15 | 115.36 (16) |
C8—C9—H9A | 109.5 | C11—C16—C8 | 123.65 (16) |
C8—C9—H9B | 109.5 | C15—C16—C8 | 120.97 (16) |
H9A—C9—H9B | 109.5 | C13—O17—H17 | 109.5 |
C6—C1—C2—C3 | −0.1 (3) | C16—C11—C12—C13 | 0.4 (3) |
C1—C2—C3—C4 | 0.3 (3) | C11—C12—C13—C14 | −0.9 (3) |
C2—C3—C4—C5 | −0.3 (3) | C11—C12—C13—O17 | −179.80 (16) |
C3—C4—C5—O7 | 178.60 (17) | C12—C13—C14—C15 | 1.4 (3) |
C3—C4—C5—C6 | 0.2 (3) | O17—C13—C14—C15 | −179.78 (16) |
C2—C1—C6—C5 | 0.0 (3) | C13—C14—C15—C16 | −1.4 (3) |
C2—C1—C6—C8 | 176.38 (17) | C12—C11—C16—C15 | −0.3 (3) |
C4—C5—C6—C1 | 0.0 (3) | C12—C11—C16—C8 | 177.69 (17) |
O7—C5—C6—C1 | −178.48 (16) | C14—C15—C16—C11 | 0.8 (3) |
C4—C5—C6—C8 | −176.53 (17) | C14—C15—C16—C8 | −177.23 (16) |
O7—C5—C6—C8 | 5.0 (3) | C10—C8—C16—C11 | 9.4 (2) |
C1—C6—C8—C10 | −108.56 (19) | C6—C8—C16—C11 | 131.57 (18) |
C5—C6—C8—C10 | 67.6 (2) | C9—C8—C16—C11 | −107.1 (2) |
C1—C6—C8—C9 | 8.9 (2) | C10—C8—C16—C15 | −172.69 (16) |
C5—C6—C8—C9 | −174.92 (16) | C6—C8—C16—C15 | −50.5 (2) |
C1—C6—C8—C16 | 127.10 (18) | C9—C8—C16—C15 | 70.8 (2) |
C5—C6—C8—C16 | −56.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7···O17i | 0.82 | 2.00 | 2.798 (2) | 163 |
O17—H17···O7ii | 0.82 | 2.18 | 2.930 (2) | 152 |
C10—H10C···O7 | 0.96 | 2.51 | 3.100 (2) | 120 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C15H16O2 |
Mr | 228.28 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 13.621 (3), 12.461 (2), 7.232 (1) |
β (°) | 93.62 (3) |
V (Å3) | 1225.0 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.50 × 0.35 × 0.04 |
Data collection | |
Diffractometer | DARCH-1 diffractometer |
Absorption correction | Part of the refinement model (ΔF) (DIFABS; Walker & Stuart, 1983) |
Tmin, Tmax | 0.966, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5620, 2810, 1589 |
Rint | 0.006 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.136, 1.14 |
No. of reflections | 2810 |
No. of parameters | 158 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.08, −0.19 |
Computer programs: DARCH software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2000), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H7···O17i | 0.82 | 2.00 | 2.798 (2) | 163 |
O17—H17···O7ii | 0.82 | 2.18 | 2.930 (2) | 152 |
C10—H10C···O7 | 0.96 | 2.51 | 3.100 (2) | 120 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, −y, −z. |
4,4'-Isopropylidenediphenol (commonly referred to as bisphenol-A or p,p-BPA), synthesized industrially by condensing phenol with acetone in the presence of an acid catalyst, is widely used as a basic material for the production of polycarbonate, epoxy and phenol resins, polyacrylates, polyesters, plastics, and coatings, and also as a colourless colour developer (Ash & Ash, 1995; Sandell et al., 1987; Okada, 1996). During the condensation, various by products, such as BPA isomers, are formed, and these are contaminants of the desired product, bisphenol A. The by product forming in the largest quantities (about 80% of all contaminants) is one of the BPA isomers, namely the title compound, (I) (also referred to as o,p-BPA; Hetper, 1991). \sch
Recently, many producers of bisphenol A have undertaken studies concerning the isomerization of this by product to p,p-BPA in the presence of strongly acid cation exchangers modified by compounds containing amino and sulfhydryl groups (Li, 1989; Takahashi & Takegami, 1993; Furumoto et al., 1993; Kawamura et al., 1994; Tasset & Wehmeyer, 1997; Heydenreich et al., 2001; Sakatani et al., 1996). The crystal structure of p,p-BPA has been known for 20 years (Belskii et al., 1983), yet no structural data have been available for o,p-BPA, nor for compounds containing the 2,4'-isopropylidenediphenol skeleton, until now. The structural differences between (I) and p,p-BPA are derived by comparison with the recently redetermined structure of p,p-BPA (Okada, 1996), with the same atom-numbering scheme used here.
The molecular structure of (I) is shown in Fig. 1. The two phenyl rings, C1—C6 and C11—C16, attached to atom C8, are planar, both with average out-of-plane deviations of 0.002 (2) Å. Methyl atoms C9 and C10 are nearly coplanar with these rings, with deviations from the ring planes of −0.060 (2) and −0.128 (2) Å, respectively. Similarly, the hydroxyl atoms O7 and O17 deviate from the ring planes by only −0.032 (1) and 0.000 (1) Å, respectively. The C1—C6 and C11—C16 ring planes are inclined at 84.81 (9)° to one another. This angle is in close agreement with the values of 86.9 (2), 83.6 (2) and 79.7 (2)° observed in the three independent A, B and C molecules of p,p-BPA, respectively, as well as with the corresponding interplanar angles observed in most of the other similar structures retrieved from the Cambridge Structural Database (CSD, Version?; Allen, 2002). CSD version ? Please give specific version number contains the results for eight different structures with the 4,4'-isopropylidenediphenol skeleton [CSD refcodes GEHJAE (Toda et al., 1988), RAWDAU (Coupar et al., 1997), RAWBOG (Ferguson et al., 1997), SIXDOS and SIXDUY (Goldberg et al., 1991), TIJVIR and TIJVEN (Eriksson & Eriksson, 2001), and UHUNAM (Takahashi et al., 2003)], which have interplanar angles in the range 80–90°, and only two with by far the smallest interplanar angles of 63.9° (BIDJED; Wang et al., 1982) and 64° (FATLER01; Eriksson & Eriksson, 2001). The bond lengths and valence angles in (I) are in similar ranges to those observed in p,p-BPA and the other above-mentioned structures. The only important difference between o,p-BPA and its p,p-isomer is the presence of one weak intramolecular hydrogen bond between methyl atom C10 and the ortho-substituted hydroxyl atom O7 (Table 1).
Regarding the close similarity of the molecular structures of the two BPA isomers, a reasonable conjecture would be that they might have rather similar crystal structures. The present investigation shows that this is not the case with respect to the packing of the molecules. Compound (I) crystallizes with four molecules in the unit cell (Fig. 2), whereas the unit cell of p,p-BPA [P21/n, a = 18.004 (8), b = 18.997 (8) and c = 11.235 (2) Å, and β = 100.86 (3)°], with a volume three times larger, contains 12 molecules, i.e. the latter contains three crystallographically independent molecules per asymmetric unit.
The molecules of (I) are linked via two hydrogen bonds (Table 1), which form infinite zigzag chains running along the c axis. The shortest intermolecular O···O contact distance in (I) [2.798 (2) Å] is somewhat longer than the shortest intermolecular O···O contact distance in p,p-BPA [2.751 (9) Å] and is similar to the corresponding shortest intermolecular O···O contact distances in other similar structures (Eriksson & Eriksson, 2001; Goldberg et al., 1991; Takahashi et al., 2003).