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The planar benzene rings in the title compound, C15H16O2, are inclined at an angle of 82.61 (9)° to one another. There are two intra­molecular hydrogen bonds of types O—H...π and C—H...O. The mol­ecules are linked by strong O—H...O hydrogen bonds into a one-dimensional network, which is compared with that of related compounds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106004070/ga1119sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106004070/ga1119Isup2.hkl
Contains datablock I

CCDC reference: 605674

Comment top

The present paper is a continuation of our structural study of compounds formed, as reaction by-products, during the industrial production of 4,4'-isopropylidenediphenol (commonly referred to as bisphenol A, BPA or p,p-BPA) by the condensation of phenol with acetone in the presence of an acid catalyst. Examples of such by-products are the isomers 2,4'-isopropylidenediphenol (o,p-BPA), the title compound 2,2'-isopropylidenediphenol [(I); o,o-BPA], and also trisphenol, polyphenols and 2,2,4-trimethyl-4-(4-hydroxyphenyl)-chromane (the so-called Dianin compound) (Kiedik et al., 1993). In a previous paper, we reported the structure of o,p-BPA [Cambridge Structural Database (Allen, 2002) refcode GALCAY (Rozycka-Sokolowska et al., 2005)]. We now compare (I) with the structures of p,p-BPA (CEGYOC02; Okada, 1996), o,p-BPA and compounds containing the 2,2`-isopropylidenediphenol skeleton, i.e. 2,2`-isopropylidene-bis(4-chloro-6-nitrophenol) (IPYCNP; Hay & Mackay, 1979) and 2,2-bis(2-hydroxy-5-methyl-3 − t-butylphenyl) propane (XMBPPR; Hardy & MacNicol, 1976).

As in the case of p,p and o,p isomers of BPA and the other above-mentioned structures, the molecule of (I) contains two planar phenyl rings, C1–C6 and C11–C16, attached to atom C8 (Fig. 1); the largest deviations from planarity are −0.009 (2) and −0.005 (2) Å for atoms C5 and C15, respectively. The dihedral angle between the planes formed by these rings is 82.61 (9)°. This angle is in close agreement with those found for the other isopropylidenediphenol isomers [84.81° for o,p-BPA, and 86.9 (2), 83.6 (2) and 79.7 (2)° for the three independent molecules of p,p-BPA], and with the values of 82.27 and 78.07° observed in XMBPPR and IPYCNP, respectively. Hydroxy atoms O7 and O17 are nearly coplanar with the C1–C6 and C11–C16 rings, with deviations from the ring planes of −0.034 (1) and 0.044 (1) Å, respectively; methyl atom C9 is 0.161 (2) Å above the plane of the C1–C6 ring and atom C10 is 0.154 (2) Å below the plane of the C11–C16 ring. The bond lengths and valence angles in (I) are within the ranges observed in the p,p and o,p isomers, and in the others compounds containing the 2,2`-isopropylidenediphenol skeleton.

There are two weak intramolecular hydrogen-bonding contacts (Table 1 and Fig. 1); the first involves hydroxy atom H17 interacting with the C1–C6 phenyl ring in a classical intramolecular O—H···π hydrogen bond (Desiraju & Steiner, 1999). The H···C distances between atom H17 and the nearest C atoms belonging to the C1–C6 phenyl ring are 2.43 (2) (for H17···C1) and 2.19 (2) Å (for H17···C6) and they are similar to the corresponding H···C distances found for 2,2-bis(2-hydroxy-5-methyl-3 − t-butylphenyl) propane, 2,6-diphenylphenol and bis(2-hydroxy-3 − t-butylphenyl) methane [XMBPPR (Hardy & MacNicol, 1976), DPPHOL (Nakatsu et al., 1978) and NISQUB (Böhmer et al., 1996), respectively]. The second C—H···O interaction between the methyl group (atom C10) and hydroxy atom O7 (Fig. 1) generates an S(6) graph-set motif (Bernstein et al., 1995). The presence of this latter weak intramolecular hydrogen bond is a common characteristic of o,p- and o,o isomers of isopropylidenediphenol and it is an important difference between them and the p,p isomer. Analysis of geometrical parameters of the intramolecular C—H···O hydrogen bonds presented here and in o,p-BPA shows a close similarity; the H···O and C···O distances and the C—H···O angle in (I) are similar to those found for the o,p-isomer [H···O = 2.51 Å, C···O = 3.100 (2) Å and C—H···O = 120° (GALCAY; Rozycka-Sokolowska et al., 2005)].

The packing structure of (I) involves one strong intermolecular hydrogen bond (Steiner, 2002) (Table 1) which links the adjacent molecules into a chain, running parallel to the [010] direction with a graph-set motif of C(8) (Bernstein et al., 1995) (Fig. 2). The two chains passing through each unit cell are antiparallel with no direction-specific interactions between the adjacent chains.

A similar one-dimensional hydrogen-bond network is found in 2,2'-diphenol (NUTSUQ; Byrne et al., 1998) and its derivatives, such as 2,2'-dihydroxy-5,5'-diallyl-biphenyl (CIPXII; Wang et al., 1983), 5,5'-di-t-butylbiphenyl-2,2'-diol and 5,5'-dimethylbiphenyl-2,2'-diol [MEBMIP and MEBMOV, respectively (Bocelli et al., 1999)]. By contrast, a totally different molecular arrangement is found in the o,p and p,p isomers of (I). The molecules of o,p-BPA are connected by two independent intermolecular O—H···O hydrogen bonds into a two-dimensional sheet of six-membered rings, which is parallel to (100), while the molecules of p,p-BPA are connected by a combination of six O—H···O and one C—H···O hydrogen bonds into a three-dimensional network built from many four- and six-membered rings. In summary, significant packing changes occur through hydrogen-bond networks found for these compounds, from three-dimensional for the p,p isomer, through two-dimensional for the o,p isomer, to a one-dimensional network here for the o,o isomer, all related to the moving of one (in o,p-BPA) or two (in o,o-BPA) hydroxy substituents from the para to the ortho position.

Experimental top

The sample of o,o-BPA was obtained from the Institute of Heavy Organic Synthesis (Kedzierzyn-Kozle, Poland). Crystals 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 C-bound H atoms were refined in geometrically idealized positions, with C—H distances of 0.93 Å (aromatic) and 0.96 Å (methyl groups), and with Uiso(H) values of 1.2 (aromatic) or 1.5 (CH3) times Ueq(C). The H atoms of hydroxy groups were located from difference maps and refined isotropically. Friedel equivalent data were merged using MERG4 in SHELXL97 (Sheldrick, 1997), according to the standard procedure for X-ray measurements of chemical compounds without atoms heavier than Si.

Computing details top

Data collection: KM4B8 (Gałdecki et al., 1996); cell refinement: KM4B8; data reduction: KM4B8; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek,2000) and Mercury1.4 (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The constituent molecule of (I), with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The dashed lines depict the intramolecular hydrogen bonds. H atoms are drawn as spheres of arbitrary radii. The centroid (Cg1) of the ring formed by C1–C6 atoms is denoted by small black circle.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing two C(8) chains of molecules lying in domains 0.05 < c < 0.45 (molecules drawn with grey lines) and 0.55 < c < 0.95 (molecules drawn with black lines) [symmetry code (i): 1 − x, −1/2 + y, 1/2 − z]. All H atoms not involved in the hydrogen bonding have been omitted for clarity.
2,2'-Isopropylidenediphenol top
Crystal data top
C15H16O2F(000) = 488
Mr = 228.28Dx = 1.216 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2abCell parameters from 35 reflections
a = 7.032 (1) Åθ = 6–20°
b = 10.419 (2) ŵ = 0.63 mm1
c = 17.017 (3) ÅT = 288 K
V = 1246.8 (4) Å3Table, colourless
Z = 40.23 × 0.21 × 0.11 mm
Data collection top
Kuma KM-4
diffractometer
Rint = 0.031
Radiation source: fine-focus sealed tubeθmax = 68.1°, θmin = 5.0°
Graphite monochromatorh = 88
ω–2θ scansk = 1012
8248 measured reflectionsl = 1420
1343 independent reflections3 standard reflections every 100 reflections
1163 reflections with I > 2σ(I) intensity decay: 1.9%
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)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.071 w = 1/[σ2(Fo2) + (0.0439P)2 + 0.0854P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
1343 reflectionsΔρmax = 0.15 e Å3
165 parametersΔρmin = 0.09 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0042 (6)
Crystal data top
C15H16O2V = 1246.8 (4) Å3
Mr = 228.28Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 7.032 (1) ŵ = 0.63 mm1
b = 10.419 (2) ÅT = 288 K
c = 17.017 (3) Å0.23 × 0.21 × 0.11 mm
Data collection top
Kuma KM-4
diffractometer
Rint = 0.031
8248 measured reflections3 standard reflections every 100 reflections
1343 independent reflections intensity decay: 1.9%
1163 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0250 restraints
wR(F2) = 0.071H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.15 e Å3
1343 reflectionsΔρmin = 0.09 e Å3
165 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. One reflection (0,2,0) was identified from refinement statistics as an outlier and omitted from the 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
O170.39327 (18)0.26163 (12)0.29360 (7)0.0484 (3)
O70.7311 (2)0.01843 (12)0.18298 (7)0.0557 (3)
C10.4967 (3)0.30348 (16)0.10850 (9)0.0459 (4)
H10.50180.39220.11420.055*
C20.3666 (3)0.25170 (19)0.05626 (10)0.0535 (5)
H20.28680.30490.02730.064*
C30.3569 (3)0.1208 (2)0.04771 (11)0.0570 (5)
H30.26910.08490.01330.068*
C40.4774 (3)0.04239 (18)0.09022 (9)0.0514 (4)
H40.47020.04620.08420.062*
C50.6090 (3)0.09462 (15)0.14169 (9)0.0420 (4)
C60.6205 (2)0.22800 (15)0.15306 (9)0.0393 (4)
C80.7634 (2)0.28554 (15)0.21121 (9)0.0420 (4)
C90.7402 (3)0.43219 (17)0.21978 (11)0.0558 (5)
H9A0.76490.47270.17020.084*
H9B0.82850.46360.25830.084*
H9C0.61280.45150.23620.084*
C100.9648 (2)0.2627 (2)0.17801 (12)0.0589 (5)
H10A0.99330.17260.17950.088*
H10B1.05590.30860.20920.088*
H10C0.97030.29260.12470.088*
C110.8911 (3)0.18601 (19)0.33816 (11)0.0563 (5)
H111.01210.18890.31610.068*
C120.8705 (3)0.1408 (2)0.41399 (11)0.0671 (6)
H120.97670.11380.44210.080*
C130.6939 (4)0.1356 (2)0.44797 (11)0.0633 (6)
H130.67980.10550.49910.076*
C140.5374 (3)0.17537 (18)0.40581 (10)0.0530 (5)
H140.41720.17230.42850.064*
C150.5588 (2)0.21977 (15)0.32982 (9)0.0414 (4)
C160.7371 (2)0.22736 (15)0.29373 (9)0.0411 (4)
H170.405 (3)0.261 (2)0.2435 (12)0.071 (7)*
H70.688 (4)0.060 (3)0.1781 (14)0.094 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O170.0408 (6)0.0561 (7)0.0483 (7)0.0024 (6)0.0027 (5)0.0003 (6)
O70.0641 (8)0.0425 (7)0.0606 (7)0.0081 (6)0.0118 (7)0.0034 (5)
C10.0480 (9)0.0465 (9)0.0433 (9)0.0069 (8)0.0022 (7)0.0064 (7)
C20.0510 (10)0.0666 (12)0.0428 (9)0.0099 (9)0.0048 (8)0.0086 (8)
C30.0592 (11)0.0696 (12)0.0421 (9)0.0063 (10)0.0091 (9)0.0028 (9)
C40.0658 (11)0.0486 (9)0.0398 (8)0.0030 (9)0.0012 (9)0.0028 (7)
C50.0469 (9)0.0429 (8)0.0362 (8)0.0038 (7)0.0012 (7)0.0019 (6)
C60.0378 (8)0.0437 (8)0.0363 (8)0.0026 (7)0.0045 (6)0.0035 (6)
C80.0389 (8)0.0429 (8)0.0443 (8)0.0016 (7)0.0003 (7)0.0032 (6)
C90.0643 (12)0.0423 (9)0.0609 (10)0.0102 (9)0.0008 (10)0.0042 (8)
C100.0413 (9)0.0774 (12)0.0579 (11)0.0019 (9)0.0043 (8)0.0058 (10)
C110.0526 (10)0.0650 (11)0.0514 (10)0.0081 (9)0.0082 (9)0.0004 (9)
C120.0726 (13)0.0780 (14)0.0505 (11)0.0123 (12)0.0146 (11)0.0066 (10)
C130.0904 (16)0.0601 (11)0.0393 (9)0.0003 (11)0.0055 (10)0.0054 (9)
C140.0666 (12)0.0474 (9)0.0448 (9)0.0058 (9)0.0072 (9)0.0022 (8)
C150.0475 (9)0.0348 (7)0.0420 (8)0.0003 (7)0.0003 (7)0.0026 (6)
C160.0440 (8)0.0381 (7)0.0414 (8)0.0002 (7)0.0032 (7)0.0015 (6)
Geometric parameters (Å, º) top
O17—C151.387 (2)C8—C91.543 (2)
O17—H170.86 (2)C9—H9A0.9600
O7—C51.3642 (19)C9—H9B0.9600
O7—H70.87 (3)C9—H9C0.9600
C1—C21.385 (3)C10—H10A0.9600
C1—C61.397 (2)C10—H10B0.9600
C1—H10.9300C10—H10C0.9600
C2—C31.373 (3)C11—C121.381 (3)
C2—H20.9300C11—C161.389 (2)
C3—C41.382 (3)C11—H110.9300
C3—H30.9300C12—C131.371 (3)
C4—C51.386 (2)C12—H120.9300
C4—H40.9300C13—C141.377 (3)
C5—C61.405 (2)C13—H130.9300
C6—C81.533 (2)C14—C151.382 (2)
C8—C161.541 (2)C14—H140.9300
C8—C101.543 (2)C15—C161.399 (2)
C15—O17—H17111.0 (16)H9A—C9—H9B109.5
C5—O7—H7106.1 (17)C8—C9—H9C109.5
C2—C1—C6122.74 (16)H9A—C9—H9C109.5
C2—C1—H1118.6H9B—C9—H9C109.5
C6—C1—H1118.6C8—C10—H10A109.5
C3—C2—C1119.19 (17)C8—C10—H10B109.5
C3—C2—H2120.4H10A—C10—H10B109.5
C1—C2—H2120.4C8—C10—H10C109.5
C2—C3—C4120.10 (18)H10A—C10—H10C109.5
C2—C3—H3120.0H10B—C10—H10C109.5
C4—C3—H3120.0C12—C11—C16122.17 (19)
C3—C4—C5120.55 (17)C12—C11—H11118.9
C3—C4—H4119.7C16—C11—H11118.9
C5—C4—H4119.7C13—C12—C11120.15 (19)
O7—C5—C4121.16 (15)C13—C12—H12119.9
O7—C5—C6117.93 (15)C11—C12—H12119.9
C4—C5—C6120.91 (16)C12—C13—C14119.49 (17)
C1—C6—C5116.50 (15)C12—C13—H13120.3
C1—C6—C8122.61 (14)C14—C13—H13120.3
C5—C6—C8120.88 (15)C13—C14—C15120.09 (18)
C6—C8—C16110.85 (13)C13—C14—H14120.0
C6—C8—C10107.76 (14)C15—C14—H14120.0
C16—C8—C10112.53 (14)C14—C15—O17115.46 (16)
C6—C8—C9112.27 (15)C14—C15—C16121.82 (17)
C16—C8—C9106.90 (14)O17—C15—C16122.65 (14)
C10—C8—C9106.51 (16)C11—C16—C15116.26 (14)
C8—C9—H9A109.5C11—C16—C8121.64 (16)
C8—C9—H9B109.5C15—C16—C8122.00 (14)
C6—C1—C2—C30.4 (3)C16—C11—C12—C130.1 (3)
C1—C2—C3—C40.7 (3)C11—C12—C13—C140.2 (3)
C2—C3—C4—C50.1 (3)C12—C13—C14—C150.1 (3)
C3—C4—C5—O7178.84 (16)C13—C14—C15—O17177.82 (17)
C3—C4—C5—C61.3 (3)C13—C14—C15—C160.8 (3)
C2—C1—C6—C50.8 (3)C12—C11—C16—C150.5 (3)
C2—C1—C6—C8179.60 (16)C12—C11—C16—C8176.07 (18)
O7—C5—C6—C1178.51 (14)C14—C15—C16—C110.9 (2)
C4—C5—C6—C11.6 (3)O17—C15—C16—C11177.76 (16)
O7—C5—C6—C81.1 (2)C14—C15—C16—C8175.65 (15)
C4—C5—C6—C8178.79 (14)O17—C15—C16—C81.2 (2)
C1—C6—C8—C16124.83 (16)C6—C8—C16—C11134.19 (17)
C5—C6—C8—C1655.6 (2)C10—C8—C16—C1113.4 (2)
C1—C6—C8—C10111.63 (18)C9—C8—C16—C11103.16 (19)
C5—C6—C8—C1067.9 (2)C6—C8—C16—C1549.4 (2)
C1—C6—C8—C95.3 (2)C10—C8—C16—C15170.19 (15)
C5—C6—C8—C9175.08 (15)C9—C8—C16—C1573.22 (19)

Experimental details

Crystal data
Chemical formulaC15H16O2
Mr228.28
Crystal system, space groupOrthorhombic, P212121
Temperature (K)288
a, b, c (Å)7.032 (1), 10.419 (2), 17.017 (3)
V3)1246.8 (4)
Z4
Radiation typeCu Kα
µ (mm1)0.63
Crystal size (mm)0.23 × 0.21 × 0.11
Data collection
DiffractometerKuma KM-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
8248, 1343, 1163
Rint0.031
(sin θ/λ)max1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.071, 1.03
No. of reflections1343
No. of parameters165
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.15, 0.09

Computer programs: KM4B8 (Gałdecki et al., 1996), KM4B8, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek,2000) and Mercury1.4 (Bruno et al., 2002).

Hydrogen bonding geometry (Å, °). top
D—H···AD—HH···AD···AD—H···A
O7—H7···O17i0.88 (3)2.00 (3)2.843 (2)160 (2)
C10—H10A···O70.962.453.031 (2)119
O17—H17···Cg10.86 (2)2.683.491159
Symmetry code: (i) 1 − x, y − 1/2, 1/2 − z.

Cg1 is the centroid of the C1–C6 ring.
 

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