Crystallographic investigations of benzothiazol-2-yl-hydrazine

Article abstract of DOI:10.1007/s10870-005-1440-4

The title compound crystallizes in the monoclinic space group P2 ₁/n with unit cell parameters a = 10.842(9), b = 5.750(7), c = 12.964(6) A, β = 110.13(6)°, V = 758.8(11) A³ and Z = 4. The final reliability index is 0.060 for 1034 observed reflections. The five-membered heterocyclic thiazole ring is coplanar with its fused benzene ring. The crystal structure is stabilized by two intermolecular N-H...N hydrogen bonded interactions.

Full text of DOI:10.1007/s10870-005-1440-4

Journal of Chemical Crystallography, Vol. 35, No. 4, April 2005 (ꢀC 2005)
DOI: 10.1007/s10870-005-1440-4
Crystallographic investigations
of benzothiazol-2-yl-hydrazine
Rajnikant,(1)∗ Dinesh,(1) Kamni,(1) M.B. Deshmukh,(2) S.S. Jagpat,(2) and S.R. Desai(2)
Received July 24, 2004; accepted November 19, 2004
The title compound crystallizes in the monoclinic space group P21/n◦with unit cell param-
3
˚
˚
eters a = 10.842(9), b = 5.750(7), c = 12.964(6) A, β = 110.13(6) , V = 758.8(11) A
and Z = 4. The final reliability index is 0.060 for 1034 observed reflections. The five-
membered heterocyclic thiazole ring is coplanar with its fused benzene ring. The crystal
structure is stabilized by two intermolecular N H · · · N hydrogen bonded interactions.
KEY WORDS: Benzothiazol; hydrazine; hydrogen bonding.
Introduction
(5.0 ml) was refluxed on water bath for 3 h, cooled,
kept overnight at room temprature. The separated
The compounds containing benzothiazole
solid was filtered and recrystallized from ethanol.
Yield-85%, m.p. 409 K. The chemical structure
assigned to the title compound as shown in Fig. 1.
was established on the basis of some chemical
studies [Elemental analysis: Found: C, 50.89%;
H, 4.27%; N, 25.43%, S, 19.41%. Spectral Char-
acteristics:IR(KBr):3100-3300(NH), 1670cm−1
(imine C N)].5
nucleus possess biological activities such as
anti-tubercular, bacteriostatic, diuretic, anti-
inflammatory, anti-viral, anti-fungal1–4 etc. The
title compound is expected to be an excellent
potential vascular (periferal) disease treatment
drug.5 In continuation to our on-going research
on the synthesis and structure determination of
nitrogen containing organic compounds6–12 and
due to importance of this class of compounds, the
crystallographic investigations of benzothiazol-2-
yl-hydrazine have been undertaken.
Three-dimensional intensity data of a well
defined single crystal of good morphology
(0.3 × 0.3 × 0.2 mm) was collected on an Enraf-
Nonius CAD-4 diffractometer (MoKα radiation,
˚
λ = 0.71073 A, ω/2θ scan mode). A total of 1333
Experimental
reflections were found to be unique (0 ≤ h ≤ 12,
0 ≤ k ≤ 6, −15 ≤ 1 ≤ 14) and 1034 reflections
were considered as observed [Fo > 4σ(Fo)]. The
reflection data were corrected for Lorentz and
polarization effects and no absorption correction
was applied.
Compound benzothiazole–2-thiol 1.67 gm
(0.01 mole) and hydrazine hydrate in ethanol
(1) Condensed Matter Physics Group, Post Graduate Department of
Physics, University of Jammu, Jammu Tawi–80 006, India.
(2) Department of Chemistry, Shivaji University, Kolhapur,
Maharashtra–416 004, India.
∗ To whom correspondence should be addressed: e-mail:
rkantverma@rediffmail.com.
The structure has been determined by us-
ing SHELXS86.13 All non-hydrogen atoms were
located from the E-map. Isotropic refinement
of the structure by least-squares method using
293
ꢀ
C
1074-1542/05/0400-0293/0 2005 Springer Science+Business Media, Inc.

294
Rajnikant, Dinesh, Kamni, Deshmukh, Jagpat, and Desai
molecule with atomic labeling (thermal ellipsoids
drawn at 50% probability) is shown in Fig. 2.16
The mean value of distances in the benzene
ring is within the normal range expected. The
Fig. 1. Chemical structure of benzothiazol-2-yl-hydrazine.
˚
two C S distances [1.760(4) and 1.743(4) A]
in the thiazole ring have values intermediate be-
3
SHELXL9314 was followed by anisotropic refine-
mentofallthenon-hydrogenatoms. Allthehydro-
gen atoms were located and the final refinement
cycle converged R-factor to 0.060. The residual
electron density in the final diff−er3ence Fourier map
tween those reported for C(sp ) S single [1.81 A]
˚
and double [1.61 A] bonds.17 A Cambridge Crys-
˚
tallographic Database search for C S bonds in
the fragment benzothiazole-2-yl attached to a ni-
trogen group was made and upon comparison
it was found that, while there is spread in the
values for the bond distances corresponding to
C11 S and C3 S in the present compound, the
majority of the values are within 3 esd of those
for the structures as presented in Table 3. The
mean value of bond angles in the five-membered
thiazol ring [108.0(1)◦] is very close to those
found in related compounds.18–21 The benzoth-
iazole nucleus adopts an almost planar conforma-
tion, with a dihedral angle of 3.34(1)◦ between
the individual planes of the benzene and thiazole
rings.
˚
ranges from 0.78 to −0.56 eA . Atomic scatter-
ing factors were taken from International Tables
for Crystallography (1992, Vol. C, Tables 4.2.6.8
and 6.1.1.4). Geometrical calculations were ob-
tained from the PC-version of PARST.15
Results and discussion
Experimental crystal data and other struc-
ture refinement parameters of the title compound
are presented in Table 1. The chemical struc-
ture assigned to the title compound is shown in
Fig. 1. Bond distances and bond angles are given
in Tables 2 and 3 presents a comparison of C11 S
and C3 S bond lengths. General view of the
The crystal structure is stabilized by
two intermolecular N1 NH1 · · · N1 and N2
NH2 · · · N4hydrogenbondedinteractions. Geom-
etry of interactions (esd’s are given in parentheses)
Table 1. Crystal Data and Structure Refinement Details
Empirical formula
CCDC No.
C7 H7 N3 S
245453
Crystal size (mm)
Temperature (K)
Radiation, wavelength (A)
Unit cell dimensions
0.3 × 0.3 × 0.2
293 (2)
˚
MoKα, 0.71073
a = 10.842(9), b = 5.750(7),
◦
˚
c = 12.964(6) A, β = 110.13(6)
3
˚
Volume
758.8(11) A
Z, Calculated density
Crystal system, space group
θ range for data collection
F(000)
4, 1.446 Mg m−3
Monoclinic, P21/n
2.12 to 24.99◦
344
Limiting indices
0 ≤ h ≤ 12, 0 ≤ k ≤ 6 , − 15 ≤ l ≤ 14
1406/1333 [R(int) = 0.0540]
Full-matrix least-squares on F2
1333/0/129
Reflections collected/unique
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [Fo > 4σ(Fo)]
R indices (all data)
1.038
R1 = 0.0603, wR2 = 0.1746
R1 = 0.0779, wR2 = 0.1937
−3
˚
Largest diff. peak and hole
0.777 and −0.555 eA

Crystallographic investigations of benzothiazol-2-yl-hydrazine
295
Table 3.Comparison of C11 S and C3 S Bond Lengths
is presented below:
Refcode∗
C11
S
C3
S
Difference
˚
˚
X
H · · · A
D[X · · · A(A)] d[H · · · A(A)] θ[X H · · · A(◦)]
BITNAT01
BAZBIN
PASYEN
QAGSUN
MOVCAB
ZENRAL
MOVBOO
YUYTUH
PIWLOW
VAPFEX
VAPFEX
GURGIJ
BITNAT10
MOVCEF
VOCMIJ
MABZTZ
NELVIJ
MEMBOV
ZENRAL
MOVBUU
HEBMAC
DUHTAB
JOLJID
HEBMAC
PIWLOW
VOCMOP
CAJWUG
HEBMAC
PIWLOW
CAJWUG
YUYTUH
GURGIJ
PIWLOW
HEBMAC
VOCMOP
VOCMIJ
PASYEN
MEMBOV
VAPFEX
BITNAT10
VAPFEX
MOVCAB
JOLJID
MABZTZ
DUHTAB
ZENRAL
BAZBIN
MOVBUU
BITNAT01
MOVBOO
ZENRAL
MOVCEF
NELVIJ
1.717
1.719
1.723
1.723
1.725
1.728
1.729
1.733
1.733
1.733
1.733
1.735
1.736
1.737
1.739
1.739
1.739
1.74
1.771
1.768
1.749
1.787
1.758
1.766
1.772
1.735
1.741
1.75
0.054
0.049
0.026
0.064
0.033
0.038
0.043
0.002
0.008
0.017
0.023
0.004
0.019
0.037
0.008
0.023
0.036
0.009
0.032
0.027
0.002
0.02
0.015
−0.013
−0.011
−0.006
−0.037
−0.013
−0.011
−0.037
0.002
0.004
0.008
0.002
−0.006
0.008
0.026
0.009
0.017
0.019
0.023
0.033
0.015
0.023
0.02
N1 NH1 · · · N1(i)
3.23 (1)
2.93 (1)
2.45 (1)
2.11 (1)
148.4 (1)
171.3 (1)
N2 NH2 · · · N4(ii)
Symmetry code: (i) −x + 1/2, y − 1/2, −z + 3/2; (ii) −x, −y − 1,
−z + 1.
The packing as shown in Fig. 3 can be de-
scribed in terms of the two unique hydrogen
bonds. The hydrogen bond from the terminal NH2
group (N1 NH1 · · · N1) generates a helical col-
umn of molecules along the b-axis related by the
21 symmetry operation. Two such columns can
be seen within the unit cell shown in Fig. 3 in
the lower left and upper right. These columns
are linked together in the a and c directions by
the second hydrogen bond from the NH group
next to the benzothiazol-2-yl to the thiazole ni-
trogen (N2 HN2 · · · N4). Two of these hydrogen
bonds form an eight-membered ring around an in-
version center. Four of these rings can be seen
at the bisectors of each cell edge in Fig. 3. An-
other view of the hydrogen bond pattern is shown
in Fig. 4. The view is approximately normal to
the bc plane. The three upper molecules are con-
nected by the (N1 NH1 · · · N1) hydrogen bond
along the b axis. The lowest molecule in the fig-
ure forms a ring about an inversion center using
two (N2 NH2 · · · N4) hydrogen bonds.
1.756
1.739
1.755
1.774
1.747
1.762
1.775
1.749
1.772
1.768
1.744
1.762
1.758
1.731
1.733
1.744
1.734
1.731
1.733
1.734
1.735
1.739
1.741
1.744
1.744
1.747
1.749
1.749
1.75
1.755
1.756
1.758
1.758
1.762
1.762
1.766
1.768
1.768
1.771
1.772
1.772
1.774
1.775
1.787
1.74
1.741
1.742
1.742
1.743
1.744
1.744
1.75
1.771
1.744
1.744
1.771
1.733
1.735
1.733
1.742
1.75
1.739
1.723
1.74
1.733
1.736
1.733
1.725
1.743
1.739
1.742
1.728
1.719
1.741
1.717
1.729
1.74
◦
˚
Table 2.Bond Distances (A) and Bond Angles ( ) for Non-hydrogen
Atoms (esd’s are Given in Parentheses)
N1 N2
N4 C3
S9 C11
C5 C6
C6 C7
C8 C11
1.415(4) N2 C3
1.302(5) N4 C10
1.743(4) S9 C3
1.385(6) C5 C10
1.379(7) C7 C8
1.394(5) C10 C11
1.343(5)
1.395(4)
1.760(4)
1.390(5)
1.385(6)
1.402(5)
0.038
0.049
0.027
0.054
0.043
0.032
0.037
0.036
0.064
C3 N2 N1
C11 S9 C3
N4 C3 S9
C6 C5 C10
C6 C7 C8
C5 C10 N4
N4 C10 C11
C8 C11 S9
117.5(3)
88.4(2)
C3 N4 C10
N4 C3 N2
N2 C3 S9
C7 C6 C5
C7 C8 C11
C5 C10 C11 119.8(3)
C8 C11 C10 121.1(4)
C10 C11 S9 109.7(3)
110.0(3)
122.7(3)
120.8(3)
121.1(4)
118.0(4)
116.5(3)
118.8(4)
121.2(4)
124.8(3)
115.4(3)
129.2(3)
1.737
1.739
1.723
QAGSUN
∗Search made for the fragment benzothiazole-2-yl-(N atom) from
the Cambridge Crystallographic Database (UK).

296
Rajnikant, Dinesh, Kamni, Deshmukh, Jagpat, and Desai
Fig. 2. ORTEP view of the molecule with thermal ellipsoids
drawn at 50% probability level.
Fig. 4. Depiction of intermolecular hydrogen bonded
The average value of D, d and θ
for the N1 NH1 · · · N1 and N2 NH2 · · · N4
intermolecular interactions is in conformity with
the theory and predictions as made for the weak
hydrogen bonds.22
interactions.
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