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The title compound, C15H12O, crystallizes in the centrosymmetric space group I41/a with one mol­ecule in the asymmetric unit. In the single hydrogen bond, the H atom is ordered, the OD...OA distance is 2.788 (1) Å and the O—H...O angle is 176 (1)°. Each hydroxyl group forms hydrogen bonds with two other hydroxyl groups and the resulting chains of interactions, in four non-linked subsets of mol­ecules, propagate along [001]. The single leading intermolecular C—H...O interaction has an H...O distance of 2.81 Å and a C—H...O angle of 140°; the single leading intramolecular C—H...O interaction has an H...O distance of 2.24 Å and a C—H...O angle of 152°. The phenanthrene core is less nearly planar in this structure than in the room temperature structure of phenanthrene-4-carboxylic acid.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100008039/bk1535sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100008039/bk1535Isup2.hkl
Contains datablock I

CCDC reference: 152641

Comment top

This report on the title compound, (I), is one of a series on hydrogen bonding and C—H···O interactions in aromatic compounds. \sch

Compound (I) crystallizes in the centrosymmetric space group I41/a with one molecule as the asymmetric unit. The refined molecule and the labelling scheme are given in Fig. 1. A single hydrogen bond and two leading C—H···O interactions (Taylor & Kennard, 1982; Steiner & Desiraju, 1998), one intramolecular, are present in this structure; geometric parameters are given in Table 2. These interactions link each molecule directly to four neighbours. The results of basic first- and second-level graph-set analysis (Bernstein et al., 1995) involving these interactions, labelled a-c for this purpose in the order of their appearance in Table 2, are given in Table 3. A l l the tabulated chains propagate along [001]. The molecules as a whole are divided into four sets, comprising those generated by space-group symmetry operators 1, 4, 5 and 8; 2, 3, 6 and 7; 9, 12, 14 and 15, and 10, 11, 13 and 16, which are `chained' within, but not between, these sets by each of the chain patterns. One example of each of these sets is included in the packing stereodiagram (Fig. 2), in which portions of the first-level a hydrogen-bond chains within these four sets are apparent.

In (I), the maximum deviations from planarity for each of the six-membered rings and the core as a whole are from ~1.2 to ~2.1 times as large as the corresponding values for the comparison molecule, phenanthrene-4-carboxylic acid, (II), at room temperature (Fitzgerald & Gerkin, 1998).

Selected bond distances and angles for (I) are given in Table 1. A l l distances and angles fall within normal limits. Corresponding pairs of chemically equivalent bonds (ignoring the substituent at C4) in the core of (I) are in good agreement, the r.m.s. difference within the seven pairs of distances being 0.008 Å. This value may be compared with the corresponding r.m.s. difference in (II) of 0.008 Å. Of the two remaining bonds in the core, C12—C13 is greater in both cases than C9—C10, by 0.124 (2) Å in (I) and by 0.132 (5) Å in (II). In (I) the closest intermolecular approaches, excluding pairs of atoms in hydrogen-bonded groups or the tabulated C—H···O interactions, are between C12 and H15Aiii [symmetry code: (iii) y − 1/4, 3/4 − x, z − 1/4] and fall short of the corresponding Bondi (1964) van der Waals radius sum by 0.06 Å. Two additional (smaller) shortfalls indicate a single noteworthy C—H···π interaction: C9—H9···(C5/C6/C7/C8/C14/C13)iv [symmetry code: (iv): 1/4 + y, 3/4 − x, −z − 1/4]. The (non-normalized) H9-centroid distance is 2.72 Å, while the H3-ring-atom distances range from 2.88 to 3.27 Å and the C9—H9···centroid angle is 161°. These values are consistent with those cited for significant C—H···π interactions, e.g. by Steiner et al. (1995).

It may be noted that, whereas in (II) approximately 4.5% of the molecules are found to be disordered (such that the substituted 4- and unsubstituted 5- positions are interchanged), in (I) there is no evidence for such disorder.

The preferential appearance of high symmetry in structures of monoalcohols has been discussed by Brock & Duncan (1994).

Experimental top

Compound (I) was obtained as a finely crystalline white powder from a sample in Dr M. S. Newman's chemical collection. Slow evaporation of an ethanolic solution of this powder at room temperature produced suitable crystals. A synthesis of (I) is described by Fierens et al. (1955).

Refinement top

Difference Fourier methods were used to locate initial H-atom positions, including the hydroxyl-H atom, and the H atoms were refined. Refined C—H distances ranged from 0.97 (1) to 1.02 (1) Å with a mean value of 0.99 (2) Å; U(H)iso values ranged from 1.0 to 1.3 times the Ueq values of the attached C atoms. The H atoms, excepting the hydroxyl-H atom, were then made canonical, with C—H = 0.98 Å and U(H)iso = 1.2Ueq of the attached C atom. In the later stages of refinement the extinction coefficient was predicted to be negative, so it was not included in the model. The maximum peak in the final difference map occurs ~0.3 Å from C10, the maximum negative peak ~0.5 Å from C15.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: TEXSAN (Molecular Structure Corporation, 1995); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN and PLATON (Spek, 1990).

Figures top
[Figure 1] Fig. 1. The refined molecule of (I) and the atom-labelling 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. A stereodiagram of (I) viewed down the c axis toward the origin. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
4-phenanthrenemethanol top
Crystal data top
C15H12ODx = 1.306 Mg m3
Mr = 208.26Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 29288 reflections
Hall symbol: -I 4adθ = 2.6–27.5°
a = 22.5868 (4) ŵ = 0.08 mm1
c = 8.3020 (1) ÅT = 150 K
V = 4235.4 (1) Å3Uncut capped column, colourless
Z = 160.38 × 0.23 × 0.23 mm
F(000) = 1760
Data collection top
Nonius KappaCCD
diffractometer
2019 reflections with I > 2σ(I)
Radiation source: X-ray tubeRint = 0.034
Graphite monochromatorθmax = 27.5°
ω scans with κ offsetsh = 2929
29288 measured reflectionsk = 2929
2431 independent reflectionsl = 610
Refinement top
Refinement on F2149 parameters
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.040Weighting scheme based on measured s.u.'s w = 1/[σ2cs + (0.034I)2]
wR(F2) = 0.102(Δ/σ)max = 0.001
S = 1.92Δρmax = 0.25 e Å3
2430 reflectionsΔρmin = 0.22 e Å3
Crystal data top
C15H12OZ = 16
Mr = 208.26Mo Kα radiation
Tetragonal, I41/aµ = 0.08 mm1
a = 22.5868 (4) ÅT = 150 K
c = 8.3020 (1) Å0.38 × 0.23 × 0.23 mm
V = 4235.4 (1) Å3
Data collection top
Nonius KappaCCD
diffractometer
2019 reflections with I > 2σ(I)
29288 measured reflectionsRint = 0.034
2431 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040149 parameters
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.92Δρmax = 0.25 e Å3
2430 reflectionsΔρmin = 0.22 e Å3
Special details top

Experimental. The Laue group assignment, the systematic absences and the centrosymmetry indicated by the intensity statistics led to assignment of the space group uniquely as I41/a (No. 88); since refinement proceeded well, it was adopted. Fourier difference methods were used to locate initial H atom positions, including the hydroxyl H atom, and the H atoms were refined. Refined C—H distances ranged from 0.97 (1) to 1.02 (1) Å, with mean value 0.99 (2) Å; their Uiso values ranged from 1.0 to 1.3 times the Ueq values of the attached C atoms. The H atoms, excepting the hydroxyl H atom, were then made canonical, with C—H = 0.98 Å and Uiso = 1.2 × Ueq of the attached C atom. In the later stages of refinement the extinction coefficient was predicted to be negative, so was not included in the model. The maximum peak in the final difference map occurs ~0.3 Å from C10, the maximum negative peak \sim 0.5 Å from C15.

Geometry. Table of Least-Squares Planes ——————————

————– Plane number 1 —————

Atoms Defining Plane Distance e.s.d. C1 (1) 0.0085 0.0010 C2 (1) −0.0287 0.0011 C3 (1) 0.0108 0.0010 C4 (1) 0.0216 0.0009 C11 (1) 0.0251 0.0009 C12 (1) −0.0338 0.0009

Mean deviation from plane is 0.0214 angstroms Chi-squared: 3693.5

————– Plane number 2 —————

Atoms Defining Plane Distance e.s.d. C5 (1) −0.0112 0.0010 C6 (1) −0.0184 0.0011 C7 (1) 0.0244 0.0011 C8 (1) 0.0071 0.0011 C13 (1) 0.0280 0.0009 C14 (1) −0.0265 0.0009

Mean deviation from plane is 0.0193 angstroms Chi-squared: 2648.7

Dihedral angles between least-squares planes plane plane angle 2 1 13.72

————– Plane number 3 —————

Atoms Defining Plane Distance e.s.d. C9 (1) 0.0392 0.0010 C10 (1) −0.0268 0.0010 C11 (1) −0.0236 0.0009 C12 (1) 0.0529 0.0009 C13 (1) −0.0462 0.0009 C14 (1) 0.0099 0.0009

Mean deviation from plane is 0.0331 angstroms Chi-squared: 8737.4

Dihedral angles between least-squares planes plane plane angle 3 1 5.85 3 2 8.11

————– Plane number 4 —————

Atoms Defining Plane Distance e.s.d. C1 (1) −0.1668 0.0010 C2 (1) −0.1156 0.0011 C3 (1) 0.1041 0.0010 C4 (1) 0.2091 0.0010 C5 (1) −0.1501 0.0010 C6 (1) −0.1782 0.0011 C7 (1) −0.0133 0.0011 C8 (1) 0.1108 0.0011 C9 (1) 0.0797 0.0010 C10 (1) −0.0482 0.0010 C11 (1) −0.0613 0.0009 C12 (1) 0.0647 0.0009 C13 (1) 0.0331 0.0009 C14 (1) 0.1024 0.0009

Additional Atoms Distance C15 (1) 0.5342

Mean deviation from plane is 0.1027 angstroms Chi-squared: 186430.9

Dihedral angles between least-squares planes plane plane angle 4 1 7.44 4 2 6.42 4 3 2.78

————– Plane number 5 —————

Atoms Defining Plane Distance e.s.d. C1 (2) 0.1668 0.0010 C2 (2) 0.1156 0.0011 C3 (2) −0.1041 0.0010 C4 (2) −0.2091 0.0010 C5 (2) 0.1501 0.0010 C6 (2) 0.1782 0.0011 C7 (2) 0.0133 0.0011 C8 (2) −0.1108 0.0011 C9 (2) −0.0797 0.0010 C10 (2) 0.0482 0.0010 C11 (2) 0.0613 0.0009 C12 (2) −0.0647 0.0009 C13 (2) −0.0331 0.0009 C14 (2) −0.1024 0.0009

Mean deviation from plane is 0.1027 angstroms Chi-squared: 186431.0

Dihedral angles between least-squares planes plane plane angle 5 1 23.66 5 2 35.58 5 3 27.83 5 4 30.37

————– Plane number 6 —————

Atoms Defining Plane Distance e.s.d. C1 (3) 0.1668 0.0010 C2 (3) 0.1156 0.0011 C3 (3) −0.1041 0.0010 C4 (3) −0.2091 0.0010 C5 (3) 0.1501 0.0010 C6 (3) 0.1782 0.0011 C7 (3) 0.0133 0.0011 C8 (3) −0.1108 0.0011 C9 (3) −0.0797 0.0010 C10 (3) 0.0482 0.0010 C11 (3) 0.0613 0.0009 C12 (3) −0.0647 0.0009 C13 (3) −0.0331 0.0009 C14 (3) −0.1024 0.0009

Mean deviation from plane is 0.1027 angstroms Chi-squared: 186431.0

Dihedral angles between least-squares planes plane plane angle 6 1 89.41 6 2 99.08 6 3 94.34 6 4 93.93 6 5 86.07

————– Plane number 7 —————

Atoms Defining Plane Distance e.s.d. C1 (4) −0.1668 0.0010 C2 (4) −0.1156 0.0011 C3 (4) 0.1041 0.0010 C4 (4) 0.2091 0.0010 C5 (4) −0.1501 0.0010 C6 (4) −0.1782 0.0011 C7 (4) −0.0133 0.0011 C8 (4) 0.1108 0.0011 C9 (4) 0.0797 0.0010 C10 (4) −0.0482 0.0010 C11 (4) −0.0613 0.0009 C12 (4) 0.0647 0.0009 C13 (4) 0.0331 0.0009 C14 (4) 0.1024 0.0009

Mean deviation from plane is 0.1027 angstroms Chi-squared: 186430.9

Dihedral angles between least-squares planes plane plane angle 7 1 85.07 7 2 88.71 7 3 87.77 7 4 86.07 7 5 93.93 7 6 30.37

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.30782 (3)0.49276 (3)0.08862 (9)0.0281 (2)
C10.42696 (5)0.48557 (5)0.4264 (1)0.0290 (3)
C20.38280 (5)0.52594 (5)0.4049 (1)0.0339 (3)
C30.36239 (4)0.53711 (5)0.2492 (1)0.0321 (3)
C40.38311 (4)0.50684 (4)0.1159 (1)0.0252 (3)
C50.42128 (5)0.41520 (4)0.1418 (1)0.0267 (3)
C60.44372 (5)0.37754 (5)0.2572 (1)0.0324 (3)
C70.49513 (5)0.34509 (5)0.2273 (1)0.0369 (3)
C80.52160 (5)0.34862 (5)0.0799 (1)0.0351 (3)
C90.52318 (4)0.38307 (4)0.2008 (1)0.0295 (3)
C100.49854 (5)0.41384 (5)0.3219 (1)0.0280 (3)
C110.45010 (4)0.45338 (4)0.2949 (1)0.0247 (3)
C120.42650 (4)0.46134 (4)0.1371 (1)0.0222 (3)
C130.44870 (4)0.42209 (4)0.0099 (1)0.0228 (3)
C140.49856 (4)0.38547 (4)0.0423 (1)0.0266 (3)
C150.35887 (5)0.52750 (4)0.0437 (1)0.0288 (3)
H10.44290.47880.53470.035*
H1O10.2891 (6)0.5136 (5)0.176 (2)0.058 (4)*
H20.36570.54680.49730.041*
H30.33210.56770.23370.038*
H50.38530.43780.16570.032*
H60.42340.37350.36090.039*
H70.51210.31990.31170.044*
H80.55720.32510.05840.042*
H90.55830.35880.22130.035*
H100.51410.40910.43140.034*
H15A0.34740.56920.03510.035*
H15B0.38950.52320.12650.035*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0251 (4)0.0278 (4)0.0313 (4)0.0012 (3)0.0045 (3)0.0053 (3)
C10.0297 (6)0.0296 (6)0.0277 (6)0.0060 (5)0.0023 (4)0.0047 (5)
C20.0334 (6)0.0315 (6)0.0368 (6)0.0016 (5)0.0008 (5)0.0118 (5)
C30.0268 (6)0.0241 (6)0.0453 (7)0.0019 (4)0.0025 (5)0.0054 (5)
C40.0226 (5)0.0190 (5)0.0340 (6)0.0044 (4)0.0018 (4)0.0006 (4)
C50.0254 (5)0.0255 (6)0.0293 (6)0.0010 (4)0.0010 (4)0.0024 (4)
C60.0340 (6)0.0349 (6)0.0282 (6)0.0020 (5)0.0028 (5)0.0015 (5)
C70.0333 (6)0.0389 (7)0.0384 (7)0.0014 (5)0.0084 (5)0.0100 (5)
C80.0250 (6)0.0356 (7)0.0446 (7)0.0049 (5)0.0021 (5)0.0056 (5)
C90.0203 (5)0.0275 (6)0.0407 (6)0.0012 (5)0.0055 (5)0.0019 (5)
C100.0257 (6)0.0267 (6)0.0316 (6)0.0048 (4)0.0073 (4)0.0023 (5)
C110.0223 (5)0.0215 (5)0.0304 (6)0.0061 (4)0.0026 (4)0.0003 (4)
C120.0184 (5)0.0191 (5)0.0291 (6)0.0050 (4)0.0000 (4)0.0017 (4)
C130.0201 (5)0.0199 (5)0.0284 (5)0.0042 (4)0.0020 (4)0.0030 (4)
C140.0202 (5)0.0241 (5)0.0356 (6)0.0028 (4)0.0009 (4)0.0002 (4)
C150.0259 (5)0.0205 (5)0.0399 (6)0.0013 (4)0.0030 (5)0.0036 (5)
Geometric parameters (Å, º) top
O1—C151.444 (1)C6—H60.98
O1—H1O10.96 (1)C7—C81.364 (2)
C1—C21.363 (2)C7—H70.98
C1—C111.412 (1)C8—C141.411 (2)
C1—H10.98C8—H80.98
C2—C31.395 (1)C9—C101.343 (1)
C2—H20.98C9—C141.430 (1)
C3—C41.382 (1)C9—H90.98
C3—H30.98C10—C111.430 (1)
C4—C121.431 (1)C10—H100.98
C4—C151.508 (1)C11—C121.426 (1)
C5—C61.377 (1)C12—C131.467 (1)
C5—C131.412 (1)C13—C141.423 (1)
C5—H50.98C15—H15A0.98
C6—C71.395 (2)C15—H15B0.98
C15—O1—H1O1106.3 (8)C10—C9—C14120.56 (9)
C2—C1—C11120.92 (9)C10—C9—H9119.7
C2—C1—H1119.5C14—C9—H9119.7
C11—C1—H1119.5C9—C10—C11121.51 (9)
C1—C2—C3118.96 (9)C9—C10—H10119.2
C1—C2—H2120.5C11—C10—H10119.2
C3—C2—H2120.5C1—C11—C10118.91 (9)
C2—C3—C4122.7 (1)C1—C11—C12120.48 (9)
C2—C3—H3118.6C10—C11—C12120.60 (9)
C4—C3—H3118.6C4—C12—C11117.35 (9)
C3—C4—C12119.25 (9)C4—C12—C13125.42 (8)
C3—C4—C15115.32 (9)C11—C12—C13117.22 (9)
C12—C4—C15125.38 (9)C5—C13—C12123.97 (9)
C6—C5—C13121.8 (1)C5—C13—C14116.85 (9)
C6—C5—H5119.1C12—C13—C14119.04 (9)
C13—C5—H5119.1C8—C14—C9119.72 (9)
C5—C6—C7120.5 (1)C8—C14—C13119.90 (9)
C5—C6—H6119.8C9—C14—C13120.26 (9)
C7—C6—H6119.8O1—C15—C4110.42 (8)
C6—C7—C8119.6 (1)O1—C15—H15A109.2
C6—C7—H7120.2O1—C15—H15B109.2
C8—C7—H7120.2C4—C15—H15A109.2
C7—C8—C14121.2 (1)C4—C15—H15B109.2
C7—C8—H8119.4H15A—C15—H15B109.5
C14—C8—H8119.4
O1—C15—C4—C393.8 (1)C5—C13—C14—C85.7 (1)
O1—C15—C4—C1289.0 (1)C5—C13—C14—C9170.37 (9)
C1—C2—C3—C43.2 (2)C6—C5—C13—C12179.71 (9)
C1—C11—C10—C9178.52 (9)C6—C5—C13—C143.9 (1)
C1—C11—C12—C45.9 (1)C6—C7—C8—C141.3 (2)
C1—C11—C12—C13173.99 (9)C7—C6—C5—C130.5 (2)
C2—C1—C11—C10176.7 (1)C7—C8—C14—C9172.8 (1)
C2—C1—C11—C121.7 (1)C7—C8—C14—C133.3 (2)
C2—C3—C4—C121.2 (2)C8—C14—C9—C10174.1 (1)
C2—C3—C4—C15176.2 (1)C8—C14—C13—C12178.25 (9)
C3—C2—C1—C112.9 (2)C9—C10—C11—C120.1 (2)
C3—C4—C12—C115.6 (1)C9—C14—C13—C125.7 (1)
C3—C4—C12—C13174.32 (9)C10—C9—C14—C132.0 (1)
C4—C12—C11—C10172.47 (8)C10—C11—C12—C137.6 (1)
C4—C12—C13—C514.4 (1)C11—C10—C9—C144.9 (2)
C4—C12—C13—C14169.89 (9)C11—C12—C4—C15171.54 (9)
C5—C6—C7—C83.2 (2)C11—C12—C13—C1410.2 (1)
C5—C13—C12—C11165.50 (9)C13—C12—C4—C158.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O1i0.96 (1)1.83 (1)2.788 (1)176 (1)
C2—H2···O1ii0.982.813.619 (1)140
C5—H5···O10.982.243.136 (1)152
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+3/4, x+1/4, z3/4.

Experimental details

Crystal data
Chemical formulaC15H12O
Mr208.26
Crystal system, space groupTetragonal, I41/a
Temperature (K)150
a, c (Å)22.5868 (4), 8.3020 (1)
V3)4235.4 (1)
Z16
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.38 × 0.23 × 0.23
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
29288, 2431, 2019
Rint0.034
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.102, 1.92
No. of reflections2430
No. of parameters149
No. of restraints?
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.25, 0.22

Computer programs: COLLECT (Nonius, 1999), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS86 (Sheldrick, 1990), TEXSAN (Molecular Structure Corporation, 1995), ORTEPII (Johnson, 1976), TEXSAN and PLATON (Spek, 1990).

Selected geometric parameters (Å, º) top
O1—C151.444 (1)C4—C151.508 (1)
C2—C1—C11120.92 (9)C9—C10—C11121.51 (9)
C1—C2—C3118.96 (9)C5—C13—C12123.97 (9)
C12—C4—C15125.38 (9)O1—C15—C4110.42 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O1i0.96 (1)1.83 (1)2.788 (1)176 (1)
C2—H2···O1ii0.982.813.619 (1)140
C5—H5···O10.982.243.136 (1)152
Symmetry codes: (i) y+3/4, x+1/4, z+1/4; (ii) y+3/4, x+1/4, z3/4.
Basic first- and second-level graph set descriptors involving interactions designated a-c in order as given in Table 2. top
abc
aC(2)C22(8)C21(8)[S(7)]
bC(6)C21(9)[S(7)]
cS(7)
 

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