Crystal and molecular structure studies of tris (2-hydroxy-3-t-butyl-5-methylbenzene)-methane trihydrate and N-benzyl-N-phenyl benzamide

Article abstract of DOI:10.1023/A:1009595123416

The structures of the title compounds, tris(2-hydroxy-3-t-butyl-5-methylbenzene)-methane (C₃₄H₄₆O₃.3H₂O, 3) and N-benzyl-N-phenylbenzamide (C₂₀H₁₇NO, 6), have been investigated by X-ray crystallography. Compound 3 crystallizes in the trigonal space group P3 with cell parameters a = 14.090(5) A, b = 14.090(5)A, c = 10.485(5)A, Z= 2. Compound 6 crystallizes in the monoclinic space group C2/c with cell parameters a = 24.533(4)A, b =9.176(4)A, c = 16.711(5)A, β= 125.88(2)°, Z= 8. Compound 3 has both intra-and intermolecular hydrogen bonds. It also exhibits a helical columnar arrangement of the molecules and goes into mesophase before melting into an isotropic liquid.

Full text of DOI:10.1023/A:1009595123416

Journal of Chemical Crystallography, Vol. 30, No. 4, 2000
Crystal and molecular structure studies of
tris(2-hydroxy-3-t-butyl-5-methylbenzene)-methane
trihydrate and N-benzyl-N-phenyl benzamide
K. S. Rangappa,(1) H. Mallesha, N. V. Anilkumar,(1) H. S. Yathirajan, M. A. Sridhar,(1)
N. K. Lokanath,(1) and J. Shashidhara Prasad(1)
Received December 7, 1999
The structures of the title compounds, tris(2-hydroxy-3-t-butyl-5-methylbenzene)-methane
(C34H46O3.3H2O, 3) and N-benzyl-N-phenylbenzamide (C20H17NO, 6), have been investi-
¯
gated by X-ray crystallography. Compound 3 crystallizes in the trigonal space group P3 with
˚
˚
˚
cellparametersa = 14.090(5)A, b = 14.090(5)A, c = 10.485(5)A, Z = 2. Compound6crystal-
˚
˚
lizes in the monoclinic space group C2/c with cell parameters a = 24.533(4)A, b = 9.176(4)A,
˚
c = 16.711(5)A, = 125.88(2) , Z = 8. Compound 3 has both intra-and intermolecular hy-
drogen bonds. It also exhibits a helical columnar arrangement of the molecules and goes into
mesophase before melting into an isotropic liquid.
KEY WORDS: THBMBM; BPB; crystal structure; helical packing; columnar packing; mesophase
transition.
Introduction
The compound
Synthesis of 6
tris(2-hydroxy-3-t-butyl-5-
N-phenylbenzylamine (4) was treated with ben-
zoylchloride (5) in alcohol with less pyridine to give
the title compound 6. The compound was recrystal-
lized from alcohol.
methylbenzene)-methane trihydrate (3, C34H46O3.
3H2O) is useful for studying the reactivity of
ambifunctional nucleophilic systems. N-benzyl-N-
phenylbenzamide (6, C20H17NO) is used in the
synthesis of polymers and also in photoreduction
processes. In view of the importance of the above
compounds, we report crystal and molecular structure
studies of 3 and 6.
The data were collected on a Rigaku AFC7S
diffractometer using MoK radiation equipped with
a graphite monochromator. Intensity data were col-
lected up to 2 = 50 using ω 2 scan method. The
data were reduced using teXsan.2 Absorption correc-
tion was not applied. The structure of 3 was solved us-
ing the program SHELXS3and refined by full-matrix
least-squares using SHELXL4 . The structure of 6 was
solved using SIR5 and refined using SHELXL.4 Hy-
drogen atoms were placed at chemically acceptable
positions and were refined as riding on the parent
atom. The data collection details along with the re-
finement details are given in Table 1.
Experimental
Synthesis of 3
5-methyl-2-tertiarybutyl-phenolmagnesiumbro-
mide (1) was treated with triethylorthoester (2) at
70 C to give compound 3. The compound1 was
recrystallized from tetrahydrofuran.
Results and discussion
(1) Department of Studies in Chemistry, Department of Studies in
Physics, University of Mysore, Manasagangotri, Mysore 570006,
The fractional atomic coordinates along with
equivalent isotropic thermal parameters and bond
India.
To whom correspondence should be addressed.
255
C
1074-1542/00/0400-0255$18.00/0 2000 Plenum Publishing Corporation

256
Rangappa, Mallesha, Anilkumar, Yathirajan, Sridhar, Lokanath, and Prasad
Table 1. Crystal Data and Structure Refinement
3
6
Empirical formula
CCDC deposit no.
Formula weight
C34H46O3.3(H2O)
CCDC-1003/5773
556.76
C20H17NO
CCDC-1003/5774
287.35
Temperature, K
566(2)
293(2)
Crystal system
Space group
Trigonal
P3
Monoclinic
C2/c
Until cell dimensions
˚
˚
˚
a =
14.090(5) A
25.433(4) A
˚
b =
14.090(5) A
9.176(4) A
16.711(5) A
˚
˚
c =
10.485(5) A
=
90
90
90
=
125.886(15)
=
120
90
3
3
˚
˚
Volume
1802.7(12) A
3159.6(16) A
Z
2
8
Density(calculated), Mg/m3
Absorption coefficient, mm
1.026
0.069 mm
1.208
0.074 mm
1
1
1
range for data collection, deg.
Reflections measured
2.56 to 24.94
1779
2.43 to 25.02
2784
Independent/observed reflections
Data/restraints/parameters
Extinction coefficient
1585 [R(int) = 0.0281] 2784[R(int) = 0.0000]
1585/0/145
0.009(8)
2784/0/200
0.0031(6)
0.973
Goodness of fit on F2
1.109
Final R indices [I > 2 (I)]
R indices (all data)
R1 = 0.0637
R1 = 0.0434
R1 = 0.0816
R1 = 0.1086
lengths and angles are given in Tables 2–5 for com-
pounds 3 and 6 respectively.
˚
Table 3. Bond Lengths (A) and Angles ( ) for Compound 3
Thethermalellipsoidplot6 ofmolecule3isshown
in Fig. 1. Figure 2 shows the molecules of 3 with
hydrogen bonds (dashed lines). The packing of the
molecules of 3 down c-axis is shown in Fig. 3. The
thermal ellipsoid plot of the molecule of 6 is shown in
Fig. 4. The packing of the molecules of 6 down b-axis
is shown in Fig. 5.
Atoms
Length
Atoms
Length
----
C1 C2
C2 C3
C2 C7
C3 C4
C4 C5
----
C4 C13
C5 O8
----
C5 C6
----
C6 C9
C9 C11
C9 C10
C9 C12
C13 C4
----
C13 C4
O1 O1
----
O1 O1
1.522(5)
1.384(4)
1.387(4)
1.386(4)
1.399(4)
1.534(3)
1.383(4)
1.397(4)
1.388(5)
1.546(4)
1.527(5)
1.528(6)
1.536(6)
1.534(3)
1.534(3)
1.743(18)
1.743(18)
----
----
----
----
----
----
----
----
----
----
----
C6 C7
Table 2. Atomic Coordinates and Equivalent Thermal Parameters
of the Nonhydrogen Atoms of the Compound 3
Intramolecular hydrogen bonds
----
----
C10 H10B
O8
2.902(7)
C11 H11A
O8
3.034(5)
Angle
Intermolecular hydrogen bonds
----
O8 H8
O8
3.049(5)
Angle
Atom
x
y
z
U
eq
Atoms
Atoms
C1
C2
C3
C4
C5
C6
C7
O8
C9
C10
C11
C12
C13
O1
0.3110(3) 0.0044(4)
0.2698(3) 0.0554(3)
0.1589(2) 0.0090(2)
0.1212(2) 0.0540(2)
0.1974(2) 0.1494(2)
0.3097(2) 0.2010(2)
0.3424(3) 0.1499(3)
0.1626(2) 0.19396(19)
0.3924(3) 0.3102(3)
0.3871(4) 0.2997(4)
0.3654(3) 0.3981(3)
0.5098(3) 0.3494(4)
0.4509(5) 0.1122(17)
0.3534(3) 0.0691(10)
0.3280(3) 0.0586(9)
0.2376(3) 0.0517(8)
0.1743(3) 0.0543(8)
0.1995(3) 0.0596(9)
0.2883(3) 0.0679(10)
0.0804(2) 0.0698(8)
0.1348(4) 0.0737(11)
0.0104(5) 0.1226(19)
0.1752(5) 0.0998(14)
0.1809(7) 0.134(2)
0.1997(5) 0.0503(12)
---- ----
C3 C2 C7
---- ----
C5 C6 C9
118.4(3)
120.9(3)
120.7(3)
121.1(3)
118.6(3)
122.5(3)
118.9(3)
117.7(3)
119.9(2)
122.4(3)
116.1(3)
122.0(3)
121.9(3)
---- ----
---- ----
C3 C2 C1
C2 C7 C6
123.4(3)
109.5(4)
106.4(3)
109.9(4)
108.4(3)
111.4(3)
111.1(3)
113.55(17)
113.55(17)
113.55(17)
60.000(9)
---- ----
---- ----
C7 C2 C1
C11 C9 C10
---- ----
---- ----
C2 C3 C4
C11 C9 C12
---- ----
---- ----
C3 C4 C5
C10 C9 C12
---- ----
C3 C4 C13
---- ----
C11 C9 C6
---- ----
---- ----
C5 C4 C13
C10 C9 C6
---- ----
O8 C5 C6
---- ----
C12 C9 C6
---- ----
----
----
O8 C5 C4
C4 C13 C4
---- ----
---- ----
C6 C5 C4
C4 C13 C4
---- ----
---- ----
C7 C6 C5
C4 C13 C4
---- ----
---- ----
C7 C6 C9
O1 O1 O1
Intramolecular hydrogen bonds
----
----
C11 H11A
C10 H10B
Intermolecular hydrogen bonds
----
124
O8
125.96
O8
123.15
0.0000
0.0000
0.5859(8) 0.307(3)
0.604(2)
0.545(13)
O8 H8
O8

Crystal and molecular structure studies
257
Table 4. Atomic Coordinates and Equivalent Thermal Parameters
of the Nonhydrogen Atoms of the Compound 6
Atom
x
y
z
Ueq
C1
C2
C3
C4
C5
C6
C7
O8
0.48778(18)
0.49777(15)
0.45749(14)
0.40811(13)
0.39877(14)
0.43846(16)
0.36090(14)
0.34568(11)
0.33249(10)
0.35758(12)
0.31625(15)
0.33875(19)
0.4008(2)
0.44218(17)
0.42016(14)
0.28059(13)
0.30500(12)
0.32201(14)
0.34342(15)
0.34806(16)
0.33156(17)
0.31017(16)
0.2419(4)
0.3556(4)
0.3737(3)
0.2763(3)
0.1614(3)
0.1454(4)
0.3127(3)
0.4407(2)
0.2046(2)
0.0593(3)
0.0580(3)
0.1984(3)
0.2227(3)
0.1065(4)
0.0357(3)
0.2473(3)
0.2859(3)
0.4282(3)
0.4639(3)
0.3594(4)
0.2196(4)
0.1815(3)
0.5255(3)
0.5860(3)
0.6157(2)
0.58643(17)
0.5264(2)
0.4950(2)
0.61028(19)
0.60725(16)
0.62820(15)
0.65891(18)
0.6098(2)
0.6410(3)
0.7198(3)
0.7694(2)
0.7390(2)
0.63870(19)
0.74222(18)
0.7764(2)
0.8714(2)
0.9334(2)
0.9011(2)
0.8056(2)
0.0765(10)
0.0731(10)
0.0578(7)
0.0439(6)
0.0541(7)
0.0686(9)
0.0476(6)
0.0687(6)
0.0433(5)
0.0420(6)
0.0557(7)
0.0703(9)
0.0745(10)
0.0681(9)
0.0515(7)
0.0520(7)
0.0446(6)
0.0554(7)
0.0650(8)
0.0673(9)
0.0742(9)
0.0624(8)
N9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
Fig. 1. ORTEP of 3 at 50% probability. The suffixes a, b, c and d
correspond to the symmetry operations 1 y, x y, z, 1 x + y,
1
x, z, y, x y, z, and x + y, x, z, respectively.
˚
Table 5. Bond Lengths (A) and Angles ( ) for Compound 6
Atoms
----
Length
Atoms
----
Length
C1 C6
1.367(5)
1.369(5)
1.386(4)
1.377(4)
1.376(4)
1.507(4)
1.392(4)
1.229(3)
1.360(3)
1.437(3)
1.482(3)
1.369(4)
C10 C11
1.388(4)
1.382(4)
1.356(5)
1.382(5)
1.394(4)
1.498(3)
1.376(4)
1.389(4)
1.383(4)
1.366(4)
1.359(5)
1.396(4)
----
----
C1 C2
C11 C12
----
----
C2 C3
----
C12 C13
----
C13 C14
C3 C4
----
----
C4 C5
C14 C15
----
----
C4 C7
----
C16 C17
----
C17 C22
C5 C6
----
----
C7 O8
C17 C18
----
----
C7 N9
----
C18 C19
----
C19 C20
N9 C10
----
----
N9 C16
C20 C21
Fig. 2. Hydrogen bonds shown as dashed lines in 3.
----
----
C10 C15
C21 C22
Atoms
Angle
Atoms
Angle
---- ----
C6 C1 C2
----
----
120.1(3)
120.0(3)
120.4(3)
119.2(2)
122.5(2)
117.7(2)
120.1(3)
120.0(3)
120.7(2)
118.8(2)
120.4(2)
125.0(2)
117.3(2)
116.3(2)
120.0(2)
120.9(2)
C11 C10 N9
119.0(2)
119.8(3)
120.6(3)
120.0(3)
120.1(3)
119.5(3)
113.8(2)
118.1(2)
120.8(2)
121.0(2)
120.9(3)
120.4(3)
119.5(3)
120.9(3)
120.2(3)
---- ----
---- ----
C1 C2 C3
C12 C11 C10
---- ----
---- ----
C4 C3 C2
C13 C12 C11
---- ----
---- ----
C5 C4 C3
C12 C13 C14
---- ----
---- ----
C5 C4 C7
C13 C14 C15
---- ----
---- ----
C3 C4 C7
C10 C15 C14
---- ----
---- ----
C4 C5 C6
N9 C16 C17
---- ----
---- ----
C1 C6 C5
C22 C17 C18
---- ----
---- ----
O8 C7 N9
C22 C17 C16
---- ----
---- ----
O8 C7 C4
C18 C17 C16
---- ----
---- ----
N9 C7 C4
C19 C18 C17
---- ----
---- ----
C7 N9 C10
C20 C19 C18
---- ----
---- ----
C7 N9 C16
C21 C20 C19
---- ----
---- ----
C10 N9 C16
C20 C21 C22
---- ----
C17 C22 C21
----
----
C15 C10 C11
---- ----
C15 C10 N9
Fig. 3. Packing of the molecules of 3 down c axis.

258
Rangappa, Mallesha, Anilkumar, Yathirajan, Sridhar, Lokanath, and Prasad
3
The packing of the molecules down c-axis (see
Figure 3) indicates a helical columnar arrangement11
of the disc-like molecules. For such an arrangement,
one can expect the presence of a liquid crystalline
phase. In fact, DSC study shows liquid crystalline
phase transition at 256.5 C and liquid crystalline to
isotropic liquid transition at 271.7 C. The phenyl ring,
comprised of atoms C2 to C7, is planar with a maxi-
˚
mum deviation of 0.015A for the atom C6. Atoms C1,
C9, and O8 also lie in the same plane.
6
The packing of molecules down b-axis (see Fig. 5)
shows a layered arrangement of the molecules. The
phenyl rings are planar. The dihedral angle between
the plane of atoms C1 to C6 and that of the atoms C17
to C22 is 57.4 . This is the same as the angle between
the plane of atoms C10 to C15 and that of the plane of
atoms C17 to C22. There are several intermolecular
distances less than Van der Waal’s radii indicating that
the intermolecular interactions are mainly due to Van
der Waal’s forces. These forces lead to a supramolec-
ular structure of the molecules.
Fig. 4. Thermal ellipsoid plot of 6 at 50% probability.
The bond lengths and bond angles in both struc-
tures are in good agreement with the values reported
for similar structures.7–10. In compound 3, both intra-
and intermolecular hydrogen bonds are observed.
The bonds lengths and angles of the hydrogen bonds
are given in Table 3.
Acknowledgments
One of the authors (KSR) would like to thank the
Department of Science and Technology (DST), Gov-
ernment of India, New Delhi, for financial assistance
under the project SP/S1/GO5/97. The authors also
thank DST for financial assistance under the project
SP/I2/FOO/93.
References
1. Cardillo, B.; Casnati, G.; Pochini, A. Chim. Ind. 1967, 49, 630.
2. TeXsan, SingleCrystalStructureAnalysisSoftware, version1.7.;
Molecular Structure Corp.: The Woodlands; TX, 1995.
3. Sheldrick, G. M. Acta Crystallogr. 1990, A46, 467.
4. Sheldrick, G.M. SHELXL97, Program for Crystal Structure
Refinement; University of Go¨ttingen: Germany, 1997.
5. Altomare, A.; Cascarano, G.; Giacovazzo, C.; Guagliardi, A.
J. Appl. Crystallogr. 1993, 26, 343.
6. Spek, A.L. Acta Crystallogr. 1990, A46, C-34.
7. Blount, J.F.; Mislow, K. Tetrahedron Lett. 1975, 11, 909.
8. Macnicol, D.D.; Mallinson, P.R.; Tominey, G. J. Chem. Res.,
Synop. 1986, 278.
9. Veldman, N.; Spek, A.L.; Schlotter, J.J.H.; Zwikker, J.W.;
Jenneskens, L.W. Acta Crystallogr. 1996, C52, 174.
10. Rajca, A.; Janicki, S. J. Org. Chem. 1994, 59, 7099.
11. Heiney, P.A.; Fontes, E.; de Jeu, W.H.; Riera, A.; Caroll, P.;
Smith, A.B. J. Phys. (Paris) 1989, 50, 461.
Fig. 5. Packing of the molecules of 6 down b-axis.