t-3-isopropyl-1-methyl-r-2,c-6-diphenylpiperidin-4-one thiosemicarbazone

Article abstract of DOI:10.1107/S010827010300917X

The piperidine ring in the title compound, C₂₂H₂₈N₄S, exhibits a chair conformation. The thiosemicarbazone moiety adopts an extended conformation, and the planar phenyl rings are oriented equatorially with respect to the p

Full text of DOI:10.1107/S010827010300917X

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
(Kirschner et al., 1966) and reductive capacity (Palenik et al.,
1974). As part of our study of thiosemicarbazone derivatives,
the title compound, (I), was prepared and the crystal structure
determined in order to establish the conformational features
of various functional groups.
ISSN 0108-2701
The bond lengths of the thiosemicarbazone moiety (Fig. 1
and Table 1) show resonance character when compared with
typical single- and double-bond lengths in cyclohexanone
thiosemicarbazone (Casas et al., 2001). Atoms C4, N10, N11,
C12, N13 and S1 are coplanar [the maximum deviation from
t-3-Isopropyl-1-methyl-r-2,c-6-
diphenylpiperidin-4-one thiosemi-
carbazone
Ê
the plane is 0.064 (19) A] and this clearly supports the
N. Sampath,a S. M. Malathy Sony,a M. N. Ponnuswamya*
and M. Nethajib
resonance effect in this moiety (see Scheme below). The
thiosemicarbazone moiety adopts an extended conformation,
as evidenced by the torsion angles listed in Table 1. The trans
con®guration of the thiocarbonyl S atom with respect to the
hydrazine N atom is evident from the S1ÐC12ÐN11ÐN10
torsion angle of 175.54 (15)ꢀ, in accordance with the
unprotonated thiosemicarbazone compounds available in the
literature (Chattopadhyay et al., 1987).
aDepartment of Crystallography and Biophysics, University of Madras, Guindy
Campus, Chennai 600 025, India, and bDepartment of Inorganic and Physical
Chemistry, Indian Institute of Science, Bangalore 560 012, India
Correspondence e-mail: mnpsy@hotmail.com
Received 11 March 2003
Accepted 24 April 2003
Online 31 May 2003
The piperidine ring in the title compound, C22H28N4S, exhibits
a chair conformation. The thiosemicarbazone moiety adopts
an extended conformation, and the planar phenyl rings are
oriented equatorially with respect to the piperidine ring. Two
intermolecular hydrogen bonds involving the S atom form
molecular pairs, and the crystal structure is stabilized by weak
CÐHÁ Á Áꢀ interactions in addition to van der Waals forces.
The C14±C19 (A) and C20±C25 (B) phenyl rings are planar
and are oriented at angles of 63.4 (7) and 81.8 (3)ꢀ, respec-
tively, to the plane of the piperidine ring. The torsion angles,
Comment
Thiosemicarbazone derivatives of Schiff base compounds
containing N,S-donor chromophores and metal complexes
exhibit non-linear optical properties (Tian et al., 1997; Duan et
al., 1996; Liu et al., 1999). These substituted thiosemi-
carbazones possess a wide range of biological activities,
including antitumour and antileukemic properties (French &
Blanz, 1966; Agarwal et al., 1972), antibacterial and antiviral
activities (Nandi et al., 1986; Chattopadhyay et al., 1987), and
antimalarial activities (Klayman et al., 1979). The antitumour
properties of heterocyclic thiosemicarbazones are partly
related to their ability to inhibit the ribonucleoside diphos-
phate reductase enzyme, which is essential in DNA synthesis
Figure 1
ZORTEP (Zsolnai, 1998) diagram of (I), showing displacement ellipsoids
at the 50% probability level.
(Moore et al., 1970). The biological activity of these N,S-donor
ligands has been correlated with their metal-chelating abilities
o346 # 2003 International Union of Crystallography
DOI: 10.1107/S010827010300917X
Acta Cryst. (2003). C59, o346±o348

organic compounds
Crystal data
asymmetry parameters and least-squares plane calculations
show that the piperidine ring adopts a chair conformation
(QT = 0.534; Nardelli, 1995). Atoms N1, C2, C4 and C5
constitute the best-®tting plane of the piperidine ring, and
C22H28N4S
Mr = 380.55
Monoclinic, P21=n
Mo Kꢂ radiation
Cell parameters from 4891
re¯ections
ꢃ = 2.0±27.9ꢀ
ꢄ = 0.16 mm
T = 293 (2) K
Ê
a = 11.1794 (17) A
1
Ê
Ê
b = 10.0720 (16) A
atoms C3 and C6 deviate by 0.652 (2) and 0.607 (2) A,
respectively, on either side of this plane.
Ê
c = 19.591 (3) A
ꢁ = 94.317 (3)ꢀ
V = 2199.7 (6) A
Needle, colorless
0.40 Â 0.36 Â 0.24 mm
The isopropyl group is equatorially substituted at the
5-position of the piperidine ring, as con®rmed by the torsion
angles (Table 1). The imine N atom is cis with respect to the
isopropyl group, and the N-methyl group is equatorially
substituted at the 1-position of the piperidine ring. Partha-
sarathi et al. (1986) reported a related structure with similar
substitution, which leads to an equatorial orientation.
3
Ê
Z = 4
Dx = 1.149 Mg m
3
Data collection
Siemens SMART CCD area-
detector diffractometer
! scans
23 481 measured re¯ections
4891 independent re¯ections
3490 re¯ections with I > 2ꢅ(I)
Rint = 0.053
ꢃmax = 27.9ꢀ
h = 14 ! 14
k = 12 ! 13
l = 25 ! 24
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.064
wR(F2) = 0.154
S = 1.07
4891 re¯ections
w = 1/[ꢅ2(F2o) + (0.0674P)2
+ 0.3252P]
where P = (F2o + 2Fc2)/30
(Á/ꢅ)max < 0.001
3
Ê
Áꢆmax = 0.31 e A
3
Ê
0.14 e A
244 parameters
H-atom parameters constrained
Áꢆmin
=
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
S1ÐC12
C4ÐN10
N10ÐN11
1.673 (2)
1.278 (2)
1.382 (2)
N11ÐC12
C12ÐN13
1.350 (2)
1.319 (3)
C4ÐN10ÐN11
C12ÐN11ÐN10
N13ÐC12ÐN11
119.13 (16)
118.66 (17)
115.74 (18)
N13ÐC12ÐS1
N11ÐC12ÐS1
124.78 (16)
119.47 (16)
Figure 2
The crystal packing of (I), viewed along the b axis. Dashed lines represent
hydrogen bonds.
C26ÐN1ÐC2ÐC3
N10ÐC4ÐC5ÐC7
C3ÐC4ÐC5ÐC7
C26ÐN1ÐC6ÐC5
C7ÐC5ÐC6ÐN1
176.42 (18)
2.8 (3)
177.23 (18)
174.69 (18)
178.01 (16)
C7ÐC5ÐC6ÐC20
56.1 (2)
177.1 (2)
3.1 (3)
C4ÐN10ÐN11ÐC12
N10ÐN11ÐC12ÐN13
N10ÐN11ÐC12ÐS1
Pairs of intermolecular NÐHÁ Á ÁS hydrogen bonds across
the center of inversion (Fig. 2) result in the formation of
dimers, a common feature that is observed in similar thio-
semicarbazone compounds (Palenik et al., 1974; Restivo &
Palenik, 1970). An intramolecular N13ÐH13AÁ Á ÁN10 hydro-
gen bond (Table 2) leads to the formation of a ®ve-membered
ring. Two CÐHÁ Á Áꢀ (Desiraju, 1989) interactions stabilize the
crystal structure in (I), viz. the C8ÐH8Á Á ÁCg1ii and C24Ð
H24Á Á ÁCg1iii interactions (see Table 2 for symmetry codes and
geometric parameters), where Cg1 is the centroid of ring A.
175.54 (15)
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
Cg1 is the centroid of the C14±C19 ring.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N13ÐH13BÁ Á ÁS1i
N13ÐH13AÁ Á ÁN10
C8ÐH8AÁ Á ÁCg1ii
C24ÐH24Á Á ÁCg1iii
0.86
0.86
0.96
0.93
2.52
2.21
3.21
3.07
3.362 (2)
2.587 (3)
4.00
167
106
142
148
3.88
Experimental
1
2
1 1
Symmetry codes: (i) 2 x; 1 y; z; (ii)
x; y
;
2 2
z; (iii) 1 ‡ x; y; z.
The title compound, (I), was synthesized by the Mannich condensa-
tion reaction. Benzaldehyde, 2-methylpentan-4-one and methylamine
in a 2:1:1 molar ratio were treated (Noller & Baliah, 1948) in ethyl
alcohol (99%), re¯uxed for 1 h and left overnight. Colorless crystals
were recrystallized from ethanol. The resulting compound was
treated with thiosemicarbazide (1 mol) in ethanol and re¯uxed for
6 h. A puri®ed sample of (I) was recrystallized from ethanol by slow
evaporation, and good quality crystals were selected for structural
studies.
All the H atoms were ®xed geometrically and allowed to ride on
their parent atoms.
Data collection: SMART (Bruker, 2000); cell re®nement: SAINT
(Bruker, 2000); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne
ꢁ
Acta Cryst. (2003). C59, o346±o348
N. Sampath et al. C22H28N4S o347

organic compounds
Desiraju, G. R. (1989). Material Science Monographs, No. 54, Crystal
Engineering ± The Design of Organic Solids, edited by G. R. Desiraju,
pp. 85±113. New York: Elsevier Science.
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pp. 3485±3490.
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
ZORTEP (Zsolnai, 1998) and PLATON (Spek, 2003); software used
to prepare material for publication: SHELXL97 and PARST
(Nardelli, 1995).
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NS would like to thank the University Grants Commission
(UGC), India, for providing a fellowship.
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Supplementary data for this paper are available from the IUCr electronic
archives (Reference: OB1115). Services for accessing these data are
described at the back of the journal.
Noller, C. R. & Baliah, V. (1948). J. Am. Chem. Soc. 70, 3853±3855.
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ꢁ
o348 N. Sampath et al.
C22H28N4S
Acta Cryst. (2003). C59, o346±o348