Synthesis, crystal structure and DFT study of 5-tert-butyl-2-hydroxy-1,3- phenylene-bis(phenylmethanone)

Article abstract of DOI:10.1007/s10870-012-0343-4

The title compound C₂₄H₂₂O₃, [common name: 4-tert-butyl-2,6-dibenzoylphenol (bdbpH)] (I), crystallizes in the orthorhombic space group P2(1)2(1)2(1) with unit cell parameters a = 7.7633(3), b = 11.4457(6) and c = 21.5319(8) A, α = β = γ = 90°, Z = 4. In the crystal structure of I, the dihedral angles between the mean planes of the central phenyl ring and the two benzene rings are 71.3(1)°and 44.9(7)°. The two benzene rings are not coplanar with dihedral angles of 42.6(7)°between them. An intramolecular O-H???O hydrogen bond is observed in the asymmetric unit. The crystal packing is stabilized by weak intermolecular C-H???O interactions. Comparison of the optimized geometries by means of a density functional theory molecular orbital theoretical calculation at the B3LYP/6-31g(d) level with the corresponding crystal structures gives support to these observations. The electronic spectra of I and 4-methyl-2,6-dibenzoylphenol (mdbpH) also predicted by the B3LYP/6-31g(d) method show some blue shifts compared with their experimental data.

Full text of DOI:10.1007/s10870-012-0343-4

J Chem Crystallogr (2012) 42:960–967
DOI 10.1007/s10870-012-0343-4
ORIGINAL PAPER
Synthesis, Crystal Structure and DFT Study
of 5-tert-Butyl-2-hydroxy-1,3-phenylene-bis(phenylmethanone)
•
Sushil K. Gupta Chanda Anjana
•
•
Neha Sen Jerry P. Jasinski James A. Golen
•
Received: 18 March 2012 / Accepted: 13 June 2012 / Published online: 6 July 2012
Ó Springer Science+Business Media, LLC 2012
Abstract The title compound C24H22O3, [common name:
4-tert-butyl-2,6-dibenzoylphenol (bdbpH)] (I), crystallizes
in the orthorhombic space group P2(1)2(1)2(1) with unit cell
parameters a = 7.7633(3), b = 11.4457(6) and c = 21.5319
of chemical research [1–3]. The title compound, 5-(tert-
butyl)-2-hydroxy-1,3-phenylene-bis(phenylmethanone) is an
important precursor, which can be used for the synthesis of
Schiff bases containing NNO donors [4, 5]. The kinetically
inert Co(III) compounds can be converted in reducing bio-
logical environments into the kinetically labile Co(II)
derivatives and provide the means for the delivery of NNO-
donor ligands, e.g. some cytotoxins, to specific locations
[6, 7]. We have reported earlier the synthesis and crystal
structure of biologically important diketones, 4-methyl-2,6-
dibenzoylphenol (mdbpH) [8]. A closely related compound
2,6-dibenzoylhydroquinone has been structurally character-
ized by Desiraju and co workers [9]. As part of our on-going
work on phenol-based Schiff base chemistry, we herein
report the synthesis, spectra and crystal structure of 5-tert-
butyl-2-hydroxy-1,3-phenylene-bis(phenylmethanone) (bdbpH)
and density functional theory (DFT) studies of mdbpH and
bdbpH. A comparison of theoretical (based on DFT MO
calculations) and experimental electronic spectra are also
presented.
˚
(8) A, a = b = c = 908, Z = 4. In the crystal structure of I,
the dihedral angles between the mean planes of the central
phenyl ring and the two benzene rings are 71.3(1)° and
44.9(7)°. The two benzene rings are not coplanar with dihedral
angles of 42.6(7)° between them. An intramolecular O–HÁÁÁO
hydrogen bond is observed in the asymmetric unit. The crystal
packing is stabilized by weak intermolecular C–HÁÁÁO inter-
actions. Comparison of the optimized geometries by means of a
density functional theory molecular orbital theoretical calcu-
lation at the B3LYP/6-31g(d) level with the corresponding
crystal structures gives support to these observations. The
electronic spectra of I and 4-methyl-2,6-dibenzoylphenol
(mdbpH) also predicted by the B3LYP/6-31g(d) method show
some blue shifts compared with their experimental data.
Keywords 4-tert-Butyl-2,6-dibenzoylphenol Á Crystal
structure Á Hydrogen bonds Á DFT MO calculations Á
Electronic absorption spectra
Experimental
Introduction
All the chemicals were of reagent grade and were used as
received. Solvents were purified by standard methods [10]
and freshly distilled prior to use.
Phenol-based Schiff bases are capable of forming metal
complexes that have important applications in several areas
Physical Measurements
S. K. Gupta Á C. Anjana Á N. Sen
School of Studies in Chemistry, Jiwaji University,
Gwalior 474 011, India
Elemental analyses were carried out on a CARLO ERBA
modal DP 200 instrument. Melting points of the compounds
in capillaries are uncorrected. The electrospray ion mass
spectra were recorded on a MICROMASS QUATTRO II
triple quadruple mass spectrometer. Infrared spectra were
J. P. Jasinski (&) Á J. A. Golen
Department of Chemistry, Keene State College,
229 Main Street, Keene, NH 03435-2001, USA
e-mail: jjasinski@keene.edu
123

J Chem Crystallogr (2012) 42:960–967
961
˚
recorded on a Shimadzu IR prestige-21 FT spectrophotom-
eter with KBr pellets (4,000–400 cm-1). Electronic spectra
in 10-3 mol L-1 CH3CN solution were obtained on a
Perkin-Elmer Lambda 35 UV–Visible spectrophotometer.
1H (300 MHz) and 13C NMR (75 MHz) measurements were
carried out on a Burker DRX-300 spectrometer in CDCl3
with chemical shifts relative to SiMe4.
[11] and graphite-monochromated Mo-Ka (k = 0.71073 A)
at 173(2) K. The structure was solved by direct methods
using SHELXS97 [12] and all of the non-hydrogen atoms
were refined anisotropically by full-matrix least-squares on
F2 using SHELXL97 [12]. H1 was located by a Fourier
difference map and refined isotropically with O1ÁÁÁH1 fixed
˚
at 0.85(2) A. All of the remaining H atoms were placed in
their calculated positions and then refined using the riding
˚
˚
Synthesis of 5-Methyl-2-hydroxy-1,3-phenylene-
model with Atom—H lengths of 0.95 A (CH) or 0.98 A
(CH3). Isotropic displacement parameters for these atoms
were set to 1.18–1.20 (CH) or 1.50 (CH3) times Ueq of the
parent atom. A multi-scan absorption correction was per-
formed using CrysAlis RED and all calculations including
molecular graphics were performed using SHELXTL [13].
The structure was refined using the twin law (10-1)(10-1)
with a BASF value of 0.14. Crystal and experimental data
for (I) are listed in Table 1. A diagram for the molecular
structure of (I) is shown in Fig. 1. Bond lengths and bond
angles are all within expected ranges (Table 2) [14].
bis(phenylmethanone)(mdbpH)(I)
The synthesis and crystal structure of the precursor mdbpH
have been published previously [8].
Synthesis of 5-tert-butyl-2-hydroxy-1,3-phenylene-
bis(phenylmethanone)(bdbpH)(I)
4-tert-Butylphenol (3.75 g, 0.025 mol) was added to anhy-
drous AlCl3 (20.0 g, 0.150 mol) dissolved in dry nitroben-
zene (30.0 ml) with stirring for 10 min. In an ice bath and
benzoyl chloride (10.5 g, 0.075 mol) was added over a
period of 1.5 h. The stirred reaction mixture was brought to
ambient temperature, stirred for 1 h and then heated to
80 °C and stirred for 8 h. The hot bath was replaced by an
ice bath and an ice cooled solution of 6 M HCl (40.0 ml)
was slowly added. The resulting mixture was allowed to
stand overnight. The organic layer was separated and was
steam distilled to remove nitrobenzene. The solid mass left
in the flask was extracted with chloroform and dried over
anhydrous NaHCO3. The chloroform solution was treated
with activated charcoal and filtered. The filtrate was allowed
to crystallize. Needle shaped crystals of the title compound
were collected by filtration and recrystallized from petro-
leum spirits with a yield of 40 %. Crystals suitable for X-ray
crystallography were grown as yellow needles by slow
evaporation from the chloroform solution (mp 419–421 K).
Composition for C24H22O3: found (calculated): C 80.20
(80.42); H, 6.07 (6.18).
Computational Details
A density functional theory (DFT) geometry optimized
molecular orbital calculation (WebMo Pro [15]) with the
GAUSSIAN-03 program package [16] employing the
B3LYP (Becke three parameter Lee–Yang–Parr exchange
correlation functional, which combines the hybrid exchange
functional of Becke [17] with the gradient-correlation
functional of Lee, Yang and Parr [18] and the 6-31g(d) basis
set [19] was performed on the title molecules. No solvent
corrections were made in these calculations. Starting
geometries were taken from X-ray refinement data. The
geometry results in the free molecule state are, therefore,
compared to those in the crystalline state. A comparison of
selected bond distances and angles in the crystal to that from
the DFT calculation is given in Table 2. Based on the opti-
mized geometries and by DFT MO calculations, electronic
spectra were predicted (Table 4). All calculations were
performed on a Workstation PC using the default conver-
gence criteria.
Positive ES-MS: m/z 359(100, MH])?. FTIR (selected,
KBr, cm-1): 3311 [m(O–H)], 1,664 [m(C=O)], 1,618
[m(C=O/H-bonded)], 1,609 [m(C–C)/ring]. UV–Vis (kmax
/
nm) (e/M-1 cm-1) (CH3CN): 248(4,324), 355(1,637), H
NMR (CDCl3): d 1.27 (s, 9H, t-butyl); d 7.48–7.65 (m,
12H, C6H5 and C6H2); d 12.16 (s,1H, OH). 13C NMR
(CDCl3): d 30.8 (CH3), 33.9 (tert-C), 122.0, 123.9, 125.9,
126.4, 126.7, 128.4, 128.8, 129.3, 130.6, 131.7, 133.1,
135.6, 137.7 (aromatic), 160.2 (C–O/phenolate), 197.3
(C=O).
1
Results and Discussion
Compound (I) was prepared by reacting 4-tert-butylphenol
and benzoyl chloride in the presence of anhydrous AlCl3 in
a 1:3:6 ratios as a yellow crystalline solid in 40 % yield
(Scheme 1).
The mass spectrum of I exhibits the molecular ion cor-
responding to [(2,6-PhCO)2C6H2(4-C(CH3)3)(OH)]. The IR
spectrum shows absorption at 1,664 and 1,618 cm-1 due to
the m(C=O) and hydrogen bonded m(C=O), respectively.
Further, a broad band appearing around 3,311 cm-1 due to
Structure Determination and Refinement
X-ray data for (I) was collected with an Oxford Diffraction
Gemini Eos CCD area detector using CrysAlisPro software
123

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J Chem Crystallogr (2012) 42:960–967
1
The H NMR spectrum of I shows a significant down-
field shift of the phenolic OH (d 12.16 ppm) due to intra-
molecular hydrogen bonding between the benzoyl oxygen
and the phenolic OH. The aromatic protons and the ali-
phatic –C(CH3)3 protons are observed as multiplets in
the 7.48–7.65 ppm region and as singlet at 1.27 ppm,
respectively.
In the 13C NMR spectrum of compound I, signals at d
197.3 (C7, C14) and 160.2 (C1) are due to the [C=O
(benzoyl) and[C–O (phenolic) carbons, respectively. The
aromatic carbons appear in the 122.0–137.7 ppm region.
The tertiary carbon and methyl carbon in the butyl group is
Table 1 Crystal and experimental data for I
Formula
C24H22O3
Formula weight
Crystal color, habit
Crystal size (mm)
Crystal system
Space group, Z
Temperature/K
358.42
Pale yellow, block
0.50 9 0.22 9 0.18
Orthorhombic
P212121, 4
173(2)
˚
a (A)
7.7633(3)
11.4457(6)
21.5319(8)
90
˚
b (A)
˚
c (A)
observed at 33.9 and 30.8 ppm, respectively. Thus, the 13
1
NMR data corroborate well with H NMR findings.
C
a (°)
b (°)
c (°)
90
90
3
˚
Volume A
1913.25(14)
760
X-ray Crystal Structure of I
F(000)
Dcalc (g cm-3
l (mm-1
)
1.244
In the title compound, C24H22O3, (I), the molecule consists
of two benzoyl groups bonded to the carbon atom at the
2,6-position of the central phenyl ring (Fig. 2). The mean
plane of the central phenyl ring (C1–C6) forms dihedral
angles of 44.9(7)° and 71.3(1)° with the mean planes of the
benzene rings (C8–C13 and C15–C20) of the benzoyl
groups, respectively. The two benzene rings are not coplanar
with dihedral angles of 42.6(7)° between them. The phenolic
)
0.081
Independent reflections/
Parameters
2,711/251
No. of reflections
[I [ 2r(I)]/R int
17,587/0.0173
2hmax (°) with MoKa
Index ranges
56.56
-10 B h B 10, -15 B k B 14,
-28 B l B 28
˚
hydrogen atom forms a hydrogen bond of length 2.557(2) A
R, Rw [I [ 2r (I)]
0.0390, 0.1131
1.133
with atom O2 of the carbonyl group, similar to that,
˚
observed in [(PhCO)2(4-Me)C6H2(OH)] [8] (2.585(19) A)
˚
and in [(PhCO)2C6H2(OH)2] [9] (2.566(3) A). In mdbpH,
Goodness-of-fit on F2
-3
˚
(Dq)max/min/e A
0.237/-0.170
Measurement
Oxford Diffraction Gemini Eos CCD
area detector
the 4-methyl substituent does not participate in intermolec-
ular hydrogen bonding, whereas in (I) the 4-tert-butyl sub-
stituent, displays weak C–HÁÁÁO intermolecular interactions
(Fig. 3, Table 3) similar to that seen in [(PhCO)2-
Program system
Structure determination
Refinement
CrysAlis Pro
SHELXS97
Full-matrix least-squares on F2
(SHELXL97)
˚
C6H2(OH)2]. The O2ÁÁÁC7 bond (1.239(2) A) is slightly
˚
longer than the O3ÁÁÁC14 bond (1.212(2) A) supporting the
observation that the O2 atom is involved as a weak inter-
molecular hydrogen-bond acceptor whereas the O3 atom is
not involved in intermolecular interactions, as described in
this molecule (Table 3). Thus crystal packing in (I) is sta-
bilized by strong O–HÁÁÁO intramolecular hydrogen bonds
(O(1)–H(1)ÁÁÁO(2)) and weak C–HÁÁÁO intermolecular
interactions (Fig. 3).
Optimized Geometry
DFT calculations were performed on mdbpH and bdbpH
(I) at the B3LYP/6-31g(d) level of theory. Starting geome-
tries were taken from X-ray refinement data. After the DFT
geometry optimization calculation on bdbpH and mdbpH,
the bond lengths and bond angles remained relatively the
same throughout the structure (Table 2). The dihedral angles
between the mean plane of the central phenyl ring and
peripheral benzene rings were calculated as 47.7(1)° and
Fig. 1 C24H22O3 (I)
m(O–H) strongly suggests the presence of intra-molecular
hydrogen bonding between the phenolic hydrogen and
benzoyl oxygen. This is confirmed by the X-ray structure
determination.
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J Chem Crystallogr (2012) 42:960–967
963
Table 2 Selected structural parameters by X-ray diffraction and theoretical calculations for mdbpH and I
˚
Bond lengths (A)
Exp.
Calc.
Bond angle (°)
Exp.
Calc.
C21H16O3 (mdbpH)
O(1)–C(1)
1.352(2)
1.240(2)
1.218(2)
1.393(3)
1.411(2)
1.404(2)
1.470(2)
1.382(2)
1.392(3)
1.507(3)
1.388(3)
1.505(2)
1.493(2)
1.385(3)
1.391(3)
1.380(3)
1.377(4)
1.377(4)
1.385(3)
1.479(3)
1.385(3)
1.392(3)
1.374(3)
1.387(3)
1.379(3)
1.380(3)
1.339
1.246
1.246
1.413
1.427
1.411
1.475
1.390
1.403
1.511
1.394
1.509
1.497
1.404
1.404
1.395
1.398
1.398
1.392
1.495
1.402
1.404
1.392
1.398
1.396
1.394
O(1)–C(1)–C(6)
O(1)–C(1)–C(2)
C(6)–C(1)–C(2)
118.04(15)
122.32(16)
119.60(16)
118.51(16)
121.50(16)
119.97(16)
122.41(16)
117.46(17)
121.53(17)
120.98(18)
122.21(17)
119.62(16)
118.45(16)
121.83(17)
120.78(16)
118.65(16)
120.57(16)
119.62(16)
118.73(17)
121.86(17)
120.1(2)
118.59
121.98
119.40
118.71
122.37
118.90
122.39
117.45
121.76
120.82
122.78
119.12
116.94
123.81
120.61
117.42
121.98
119.27
117.76
122.88
120.25
120.14
119.93
120.05
120.43
120.35
120.43
121.29
119.27
122.68
117.92
120.41
120.01
119.96
120.06
120.26
O(2)–C(8)
O(3)–C(15)
C(1)–C(6)
C(3)–C(2)–C(1)
C(1)–C(2)
C(3)–C(2)–C(8)
C(2)–C(3)
C(1)–C(2)–C(8)
C(2)–C(8)
C(4)–C(3)–C(2)
C(3)–C(4)
C(3)–C(4)–C(5)
C(4)–C(5)
C(3)–C(4)–C(7)
C(4)–C(7)
C(4)–C(5)–C(7)
C(5)–C(6)
C(6)–C(5)–C(4)
C(6)–C(15)
C(8)–C(9)
C(5)–C(6)–C(1)
C(5)–C(6)–C(15)
C(1)–C(6)–C(15)
O(2)–C(8)–C(2)
O(2)–C(8)–C(9)
C(2)–C(8)–C(9)
C(9)–C(14)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
C(12)–C(13)
C(13)–C(14)
C(15)–C(16)
C(16)–C(21)
C(16)–C(17)
C(17)–C(18)
C(18)–C(19)
C(19)–C(20)
C(20)–C(21)
C(14)–C(9)–C(10)
C(14)–C(9)–C(8)
C(10)–C(9)–C(8)
C(11)–C(10)–C(9)
C(12)–C(11)–C(10)
C(11)–C(12)–C(13)
C(12)–C(13)–C(14)
C(13)–C(14)–C(9)
O(3)–C(15)–C(16)
O(3)–C(15)–C(6)
C(16)–C(15)–C(6)
C(21)–C(16)–C(17)
C(21)–C(16)–C(15)
C(17)–C(16)–C(15)
C(18)–C(17)–C(16)
C(17)–C(18)–C(19)
C(18)–C(19)–C(20)
C(19)–C(20)–C(21)
C(20)–C(21)–C(16)
119.9(2)
120.7(2)
119.6(2)
120.3(2)
121.19(17)
118.49(18)
120.26(16)
118.71(18)
122.52(17)
118.72(18)
120.3(2)
120.4(2)
119.9(2)
119.8(2)
120.81(19)
C24H22O3 (I)
O(1)–C(1)
O(2)–C(7)
O(3)–C(14)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(2)–C(14)
C(3)–C(4)
C(4)–C(5)
C(4)–C(21)
1.343(2)
1.239(2)
1.212(2)
1.398(2)
1.412(2)
1.387(3)
1.511(2)
1.404(2)
1.387(2)
1.528(3)
1.339
1.246
1.226
1.412
1.425
1.394
1.509
1.406
1.392
1.539
O(1)–C(1)–C(2)
O(1)–C(1)–C(6)
C(2)–C(1)–C(6)
C(3)–C(2)–C(1)
C(3)–C(2)–C(14)
C(1)–C(2)–C(14)
C(2)–C(3)–C(4)
C(5)–C(4)–C(3)
C(5)–C(4)–C(21)
C(3)–C(4)–C(21)
118.28(16)
122.61(16)
119.07(16)
119.67(16)
119.36(16)
120.93(16)
122.56(16)
116.68(16)
122.67(17)
120.65(16)
118.78
122.11
119.08
119.13
116.88
123.86
123.26
116.53
123.39
120.08
123

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J Chem Crystallogr (2012) 42:960–967
Table 2 continued
˚
Bond lengths (A)
Exp.
Calc.
Bond angle (°)
Exp.
Calc.
C(5)–C(6)
1.404(3)
1.476(2)
1.493(2)
1.392(2)
1.393(2)
1.382(3)
1.383(3)
1.380(3)
1.384(3)
1.490(2)
1.386(3)
1.384(3)
1.384(3)
1.383(4)
1.372(3)
1.391(3)
1.512(3)
1.539(3)
1.535(3)
1.412
1.475
1.498
1.404
1.404
1.395
1.396
1.398
1.392
1.495
1.402
1.404
1.392
1.398
1.396
1.394
1.510
1.547
1.547
C(4)–C(5)–C(6)
122.47(16)
119.02(16)
122.65(16)
118.32(17)
120.17(16)
118.38(16)
121.44(16)
119.46(16)
118.07(16)
122.31(15)
120.04(17)
120.05(19)
120.35(18)
119.96(17)
120.10(18)
121.11(16)
119.11(16)
119.68(15)
119.62(17)
121.62(16)
118.69(17)
119.69(19)
120.1(2)
122.72
118.96
122.16
118.86
120.66
117.40
121.93
119.17
117.96
122.17
120.76
120.13
119.92
120.06
120.42
120.30
118.34
121.25
119.27
122.65
117.95
120.41
119.96
120.00
120.06
120.29
112.15
108.19
109.48
108.26
109.42
109.29
C(6)–C(7)
C(5)–C(6)–C(1)
C(7)–C(8)
C(5)–C(6)–C(7)
C(8)–C(13)
C(8)–C(9)
C(1)–C(6)–C(7)
O(2)–C(7)–C(6)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
C(12)–C(13)
C(14)–C(15)
C(15)–C(20)
C(15)–C(16)
C(16)–C(17)
C(17)–C(18)
C(18)–C(19)
C(19)–C(20)
C(21)–C(24)
C(21)–C(23)
C(21)–C(22)
O(2)–C(7)–C(8)
C(6)–C(7)–C(8)
C(13)–C(8)–C(9)
C(13)–C(8)–C(7)
C(9)–C(8)–C(7)
C(10)–C(9)–C(8)
C(9)–C(10)–C(11)
C(12)–C(11)–C(10)
C(11)–C(12)–C(13)
C(12)–C(13)–C(8)
O(3)–C(14)–C(15)
O(3)–C(14)–C(2)
C(15)–C(14)–C(2)
C(20)–C(15)–C(16)
C(20)–C(15)–C(14)
C(16)–C(15)–C(14)
C(17)–C(16)–C(15)
C(18)–C(17)–C(16)
C(19)–C(18)–C(17)
C(18)–C(19)–C(20)
C(15)–C(20)–C(19)
C(24)–C(21)–C(4)
C(24)–C(21)–C(23)
C(4)–C(21)–C(23)
C(24)–C(21)–C(22)
C(4)–C(21)–C(22)
C(23)–C(21)–C(22)
120.54(19)
119.7(2)
120.26(18)
111.97(19)
110.1(3)
108.73(19)
107.9(2)
110.03(16)
108.1(2)
61.4(2)°, slightly twisted from that observed in the crystals
at 44.97(7)° and 71.29(6)° for bdbpH. Similarly, the DFT
values for the dihedral angles between the central phenyl
ring and peripheral benzene rings for mdbpH were calcu-
lated as 47.0(6)° and 61.5(2)°, respectively, as compared to
54.11(6)°, 74.32(5)° in the crystal. The dihedral angle
between the mean planes of the two benzene rings of the
benzoyl groups were calculated as 28.13° (bdbpH) and
28.24° (mdbpH) compared with those of the single crystal
values, 42.67(6)° (bdbpH) and 27.04(10)° (mdbpH),
clearly suggesting that these are not coplanar and that the
presence of a t-propyl group in the para position of the
central phenyl ring bdbpH plays a significant role in
C–HÁÁÁO hydrogen bonding, intermolecular interactions and
crystal packing when compared to that of the methyl group
similarly placed in mdbpH.
Electronic Absorption Spectra
The theoretical DFT calculations using the B3LYP/
6-31g(d) basis set for mdbpH and bdbpH show that each
has two absorptions, which are consistent with the exper-
imental data (Table 4). The first predicted band at 284 nm
in mdbpH and 293 nm in bdbpH exhibit some blue shifts
compared to the experimental data. However, the second
predicted band at 257 nm in mdbpH and 259 nm in
bdbpH display some red shift in comparison with the
experimental values. For mdbpH and bdbpH, the bands in
123

J Chem Crystallogr (2012) 42:960–967
965
Scheme 1 Synthesis of 5-tert-butyl-2-hydroxy-1,3-phenylenebis(phenylmethanone)
Fig. 2 Molecular structure of
C24H22O3 (I), with the atom
labelling scheme of the
asymmetric unit and 50 %
probability displacement
ellipsoids of non-H atoms
Fig. 3 Crystal packing of
C24H22O3 (I) viewed along the
a axis. Dashed lines indicate the
strong O–HÁÁÁO intramolecular
hydrogen bond and weak
C–HÁÁÁO intermolecular
interactions
123

966
J Chem Crystallogr (2012) 42:960–967
Fig. 4 Surfaces of the frontier
molecular orbitals for mdbpH
and I
HOMO
HOMO
LUMO
LUMO
LUMO +1
LUMO +1
˚
Table 3 Hydrogen bond and intermolecular interactions for compound (I) (A and °)
D–HÁÁÁA
d(D–H)
d(HÁÁÁA)
d(DÁÁÁA)
\(DHA)
O(1)–H(1)ÁÁÁO(2)
C(9)–H(9A)ÁÁÁO(2)#1
C(12)–H(12A)ÁÁÁO(3)#2
0.835(17)
0.95
1.80(2)
2.51
2.557(2)
3.350(2)
3.407(2)
150(3)
147.1
166.4
0.95
2.48
Symmetry transformations used to generate equivalent atoms: #1 -x ? 1, y ? 1/2, -z ? 3/2; #2 -x ? 1, y - 1/2, -z ? 3/2
the visible region (352–355 nm) are assigned to phenolato
O- to phenyl charge transfer transition while the other
bands (248–257 nm) are assigned to carbonyl p ? p*
transitions. The calculated oscillator strengths for the
absorptions qualitatively agree with the measured molar
absorptivities for these transitions. Predicted surfaces of the
frontier molecular orbitals of mdbpH and bdbpH are
shown in Fig. 4. For mdbpH and bdbpH, as seen from
Fig. 4, in the HOMO, electronic density is distributed on
the central phenyl ring containing oxygen, in the LUMO,
electronic density is distributed on the carbonyl group and
central phenyl ring and in the LUMO ? 1, electronic
density is mainly delocalized on one benzoyl group. The
lowest energy transition observed in the experimental
spectrum correlates with the HOMO–LUMO gap and the
higher energy absorption correlates with the HOMO–
LUMO ? 1 transition. The calculated oscillator strengths
for the absorptions qualitatively agree with the measured
molar absorptivities for these transitions. It is evident,
therefore, that electron transitions among the frontier
123

J Chem Crystallogr (2012) 42:960–967
967
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CCDC 857168 contains supplementary crystallographic
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via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The
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Acknowledgments SKG thanks DST for financial assistance (Grant
No. SR/S1/IC-38/2007) and USIEF for the award of a Fulbright-
Nehru Senior Research Fellowship. JPJ acknowledges the NSF–MRI
(Grant No. CHE1039027) for funds to purchase the X-ray
diffractometer.
123