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Molecules of the title compound [systematic name: 2,4′-(propane-2,2-diyl)diphenol], C15H16O2, are linked through intermolecular O—H...O hydrogen bonds into infinite zigzag chains. The molecular structure is compared with that of the related compound 4,4′-iso­propyl­idene­diphenol.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010403015X/ga1076sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S010827010403015X/ga1076Isup2.hkl
Contains datablock I

CCDC reference: 263062

Comment top

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).

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The unit-cell contents of (I), showing one set of intermolecular hydrogen bonds as dashed lines. All C-bound H atoms have been omitted for clarity. [Symmetry codes are as given in Table 1.]
2,4'-(propane-2,2-diyl)diphenol top
Crystal data top
C15H16O2F(000) = 488
Mr = 228.28Dx = 1.238 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 20 reflections
a = 13.621 (3) Åθ = 8–15°
b = 12.461 (2) ŵ = 0.08 mm1
c = 7.232 (1) ÅT = 293 K
β = 93.62 (3)°Plate, colourless
V = 1225.0 (4) Å30.50 × 0.35 × 0.04 mm
Z = 4
Data collection top
DARCH-1
diffractometer
1589 reflections with I > 2σ(I)
Radiation source: BSW x-ray tubeRint = 0.006
Graphite monochromatorθmax = 27.4°, θmin = 1.5°
ω/2θ scansh = 1717
Absorption correction: part of the refinement model (ΔF)
(DIFABS; Walker & Stuart, 1983)
k = 1616
Tmin = 0.966, Tmax = 0.996l = 99
5620 measured reflections3 standard reflections every 100 reflections
2810 independent reflections intensity decay: 2.2%
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)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.136H-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 parametersΔρmax = 0.08 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C15H16O2V = 1225.0 (4) Å3
Mr = 228.28Z = 4
Monoclinic, P21/cMo Kα radiation
a = 13.621 (3) ŵ = 0.08 mm1
b = 12.461 (2) ÅT = 293 K
c = 7.232 (1) Å0.50 × 0.35 × 0.04 mm
β = 93.62 (3)°
Data collection top
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 = 0.9963 standard reflections every 100 reflections
5620 measured reflections intensity decay: 2.2%
2810 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.136H-atom parameters constrained
S = 1.14Δρmax = 0.08 e Å3
2810 reflectionsΔρmin = 0.19 e Å3
158 parameters
Special details top

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
C10.41329 (13)0.03795 (15)0.2452 (2)0.0906 (5)
H10.44890.02580.24940.109*
C20.45624 (13)0.12856 (14)0.1752 (3)0.0912 (5)
H20.51930.12470.13340.109*
C30.40668 (13)0.22299 (15)0.1672 (2)0.0961 (5)
H30.43570.28400.12060.115*
C40.31466 (13)0.22779 (16)0.2277 (3)0.0981 (5)
H40.28060.29250.22160.118*
C50.27073 (13)0.13841 (14)0.2979 (3)0.0890 (4)
C60.31862 (13)0.03781 (14)0.3102 (2)0.0897 (4)
O70.17594 (9)0.14379 (10)0.35549 (19)0.0960 (4)
H70.16600.20380.39680.144*
C80.27151 (13)0.05871 (14)0.3980 (2)0.0882 (4)
C90.33327 (14)0.16039 (16)0.3794 (3)0.1017 (5)
H9A0.30050.22000.43260.153*
H9B0.34140.17440.25070.153*
H9C0.39660.15050.44320.153*
C100.26617 (13)0.03819 (14)0.6043 (2)0.0933 (5)
H10A0.23940.10020.66190.140*
H10B0.33100.02410.65870.140*
H10C0.22470.02270.62260.140*
C110.08672 (14)0.09981 (15)0.3934 (3)0.0947 (5)
H110.09060.09440.52190.114*
C120.00174 (14)0.12450 (14)0.3048 (3)0.0959 (5)
H120.05630.13590.37350.115*
C130.01109 (13)0.13264 (13)0.1157 (3)0.0866 (4)
C140.07046 (14)0.11704 (15)0.0172 (3)0.0949 (5)
H140.06610.12370.11110.114*
C150.15901 (13)0.09135 (15)0.1094 (3)0.0925 (5)
H150.21330.07950.04040.111*
C160.17051 (12)0.08251 (13)0.3007 (2)0.0846 (4)
O170.10262 (8)0.15825 (11)0.03339 (18)0.0951 (4)
H170.10370.14460.07760.143*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0813 (9)0.0976 (11)0.0931 (11)0.0075 (8)0.0080 (8)0.0022 (8)
C20.0857 (10)0.0958 (11)0.0952 (11)0.0056 (8)0.0062 (8)0.0010 (9)
C30.0920 (11)0.0985 (12)0.0964 (11)0.0049 (9)0.0057 (9)0.0184 (9)
C40.0896 (10)0.0954 (11)0.1081 (12)0.0042 (9)0.0038 (9)0.0135 (10)
C50.0769 (9)0.0997 (11)0.0903 (10)0.0002 (8)0.0047 (8)0.0014 (8)
C60.0843 (10)0.0956 (11)0.0886 (10)0.0001 (8)0.0019 (8)0.0004 (8)
O70.0874 (7)0.0885 (7)0.1129 (10)0.0064 (5)0.0129 (6)0.0011 (6)
C80.0849 (10)0.0865 (10)0.0916 (10)0.0029 (7)0.0059 (8)0.0017 (8)
C90.0987 (12)0.1046 (13)0.1004 (13)0.0124 (10)0.0042 (10)0.0001 (10)
C100.0922 (11)0.0912 (11)0.0947 (11)0.0004 (8)0.0090 (9)0.0033 (8)
C110.0958 (11)0.1038 (12)0.0843 (10)0.0112 (9)0.0052 (9)0.0002 (8)
C120.0884 (11)0.1013 (12)0.0988 (12)0.0065 (9)0.0118 (9)0.0014 (9)
C130.0818 (9)0.0813 (9)0.0949 (11)0.0067 (7)0.0079 (8)0.0035 (8)
C140.0962 (12)0.0982 (12)0.0905 (11)0.0066 (9)0.0068 (9)0.0009 (9)
C150.0871 (10)0.0964 (11)0.0947 (11)0.0061 (8)0.0106 (8)0.0008 (9)
C160.0879 (10)0.0785 (9)0.0869 (9)0.0012 (7)0.0016 (8)0.0017 (7)
O170.0828 (7)0.1016 (8)0.0992 (8)0.0136 (6)0.0076 (6)0.0091 (7)
Geometric parameters (Å, º) top
C1—C21.382 (2)C9—H9B0.9600
C1—C61.400 (2)C9—H9C0.9600
C1—H10.9300C10—H10A0.9600
C2—C31.356 (3)C10—H10B0.9600
C2—H20.9300C10—H10C0.9600
C3—C41.354 (2)C11—C121.363 (2)
C3—H30.9300C11—C161.377 (2)
C4—C51.377 (2)C11—H110.9300
C4—H40.9300C12—C131.370 (3)
C5—O71.383 (2)C12—H120.9300
C5—C61.413 (2)C13—C141.371 (2)
C6—C81.521 (2)C13—O171.384 (2)
O7—H70.8200C14—C151.379 (2)
C8—C101.520 (2)C14—H140.9300
C8—C91.532 (3)C15—C161.387 (2)
C8—C161.534 (2)C15—H150.9300
C9—H9A0.9600O17—H170.8200
C2—C1—C6122.96 (16)C8—C9—H9C109.5
C2—C1—H1118.5H9A—C9—H9C109.5
C6—C1—H1118.5H9B—C9—H9C109.5
C3—C2—C1120.22 (17)C8—C10—H10A109.5
C3—C2—H2119.9C8—C10—H10B109.5
C1—C2—H2119.9H10A—C10—H10B109.5
C4—C3—C2119.53 (17)C8—C10—H10C109.5
C4—C3—H3120.2H10A—C10—H10C109.5
C2—C3—H3120.2H10B—C10—H10C109.5
C3—C4—C5121.07 (18)C12—C11—C16122.82 (18)
C3—C4—H4119.5C12—C11—H11118.6
C5—C4—H4119.5C16—C11—H11118.6
C4—C5—O7120.51 (16)C11—C12—C13120.63 (18)
C4—C5—C6122.09 (17)C11—C12—H12119.7
O7—C5—C6117.39 (15)C13—C12—H12119.7
C1—C6—C5114.14 (15)C14—C13—C12118.76 (17)
C1—C6—C8124.27 (16)C14—C13—O17123.15 (17)
C5—C6—C8121.50 (16)C12—C13—O17118.08 (18)
C5—O7—H7109.5C13—C14—C15119.65 (18)
C10—C8—C6108.93 (14)C13—C14—H14120.2
C10—C8—C9106.63 (15)C15—C14—H14120.2
C6—C8—C9111.65 (15)C14—C15—C16122.77 (17)
C10—C8—C16112.69 (15)C14—C15—H15118.6
C6—C8—C16110.56 (14)C16—C15—H15118.6
C9—C8—C16106.34 (14)C11—C16—C15115.36 (16)
C8—C9—H9A109.5C11—C16—C8123.65 (16)
C8—C9—H9B109.5C15—C16—C8120.97 (16)
H9A—C9—H9B109.5C13—O17—H17109.5
C6—C1—C2—C30.1 (3)C16—C11—C12—C130.4 (3)
C1—C2—C3—C40.3 (3)C11—C12—C13—C140.9 (3)
C2—C3—C4—C50.3 (3)C11—C12—C13—O17179.80 (16)
C3—C4—C5—O7178.60 (17)C12—C13—C14—C151.4 (3)
C3—C4—C5—C60.2 (3)O17—C13—C14—C15179.78 (16)
C2—C1—C6—C50.0 (3)C13—C14—C15—C161.4 (3)
C2—C1—C6—C8176.38 (17)C12—C11—C16—C150.3 (3)
C4—C5—C6—C10.0 (3)C12—C11—C16—C8177.69 (17)
O7—C5—C6—C1178.48 (16)C14—C15—C16—C110.8 (3)
C4—C5—C6—C8176.53 (17)C14—C15—C16—C8177.23 (16)
O7—C5—C6—C85.0 (3)C10—C8—C16—C119.4 (2)
C1—C6—C8—C10108.56 (19)C6—C8—C16—C11131.57 (18)
C5—C6—C8—C1067.6 (2)C9—C8—C16—C11107.1 (2)
C1—C6—C8—C98.9 (2)C10—C8—C16—C15172.69 (16)
C5—C6—C8—C9174.92 (16)C6—C8—C16—C1550.5 (2)
C1—C6—C8—C16127.10 (18)C9—C8—C16—C1570.8 (2)
C5—C6—C8—C1656.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7···O17i0.822.002.798 (2)163
O17—H17···O7ii0.822.182.930 (2)152
C10—H10C···O70.962.513.100 (2)120
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y, z.

Experimental details

Crystal data
Chemical formulaC15H16O2
Mr228.28
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)13.621 (3), 12.461 (2), 7.232 (1)
β (°) 93.62 (3)
V3)1225.0 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.50 × 0.35 × 0.04
Data collection
DiffractometerDARCH-1
diffractometer
Absorption correctionPart of the refinement model (ΔF)
(DIFABS; Walker & Stuart, 1983)
Tmin, Tmax0.966, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections
5620, 2810, 1589
Rint0.006
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.136, 1.14
No. of reflections2810
No. of parameters158
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.08, 0.19

Computer programs: DARCH software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2000), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O7—H7···O17i0.822.002.798 (2)163
O17—H17···O7ii0.822.182.930 (2)152
C10—H10C···O70.962.513.100 (2)120
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x, y, z.
 

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