Synthesis and structures of two N,N′-bis(2-pyridinyl)thioureas and N-(2-pyridinyl)-N′-(benzoyl)thiourea

Article abstract of DOI:10.1016/S0022-2860(01)00655-X

N,N-′bis(4,6-lutidyl)thiourea, (4,6Lut)₂Tu, triclinic, P-1, a = 7.4930(8), b = 8.7210(8), c = 12.6040(14) ?, α = 93.437(5), β = 94.919(5), γ = 110.246(5)°, V = 766.35(14) ?³ and Z = 2; N,N′-bis(5-picolyl)thiourea, (5Pic)₂Tu, monoclinic, P2₁/c, a = 17.205(2), b = 4.4970(5), c = 17.425(2) ?, β = 117.763(5)°, V = 1272.6(3) ?³ and Z = 4 and N-(2-pyridyl)-N′-benzoylthiourea, PyTubenzo, monoclinic, P2₁/n, a = 5.345(3), b = 20.343(6), c = 11.808(2) ?, β = 90.23(3)°, V = 1290.8(1) ?³ and Z = 4. Intramolecular hydrogen bonding between N′H and the pyridyl nitrogen, intermolecular hydrogen bonding involving the thione sulfur and the NH hydrogen, and the planarity of the molecule is affected by substitution on the pyridine rings of the bis(2-pyridyl)thioureas. PyTubenzo has intramolecular hydrogen bonding to the carbonyl oxygen, intermolecular hydrogen bonding to a thione sulfur and is the least planar of the molecules under study. ¹H NMR studies in CDCl₃ show the NH′ hydrogen resonance considerably downfield from other resonances in the spectrum of the bis(2-pyridyl)thioureas.

Full text of DOI:10.1016/S0022-2860(01)00655-X

Journal of Molecular Structure 605 (2002) 9±15
www.elsevier.com/locate/molstruc
Synthesis and structures of two N,N0-bis(2-pyridinyl)thioureas and
N-(2-pyridinyl)-N0-(benzoyl)thiourea
*
Werner Kaminsky, Karen I. Goldberg, Douglas X. West
Department of Chemistry, University of Washington, Box 351700, Seattle, WA 98195-1700, USA
Received 5 March 2001; accepted 2 May 2001
Abstract
0
ꢀ
N,N- bis(4,6-lutidyl)thiourea, (4,6Lut)2Tu, triclinic, P-1, a ˆ 7:4930ꢀ8†; b ˆ 8:7210ꢀ8†; c ˆ 12:6040ꢀ14† A; a ˆ 93:437ꢀ5†;
b ˆ 94:919ꢀ5†; g ˆ 110:246ꢀ5†8; V ˆ 766:35ꢀ14† A and Z ˆ 2; N,N0-bis(5-picolyl)thiourea, (5Pic)2Tu, monoclinic, P21/c,
ꢀ 3
a ˆ 17:205ꢀ2†; b ˆ 4:4970ꢀ5†; c ˆ 17:425ꢀ2† A; b ˆ 117:763ꢀ5†8; V ˆ 1272:6ꢀ3† A and Z ˆ 4 and N-(2-pyridyl)-N0-
ꢀ
ꢀ 3
ꢀ
benzoylthiourea, PyTubenzo, monoclinic, P21/n, a ˆ 5:345ꢀ3†; b ˆ 20:343ꢀ6†; c ˆ 11:808ꢀ2† A; b ˆ 90:23ꢀ3†8; V ˆ
0
ꢀ 3
1290:8ꢀ1† A and Z ˆ 4: Intramolecular hydrogen bonding between N H and the pyridyl nitrogen, intermolecular hydrogen
bonding involving the thione sulfur and the NH hydrogen, and the planarity of the molecule is affected by substitution on the
pyridine rings of the bis(2-pyridyl)thioureas. PyTubenzo has intramolecular hydrogen bonding to the carbonyl oxygen, inter-
1
molecular hydrogen bonding to a thione sulfur and is the least planar of the molecules under study. H NMR studies in CDCl3
show the NH0 hydrogen resonance considerably down®eld from other resonances in the spectrum of the bis(2-pyridyl)thioureas.
q 2002 Elsevier Science B.V. All rights reserved.
Keywords: Bis(2-pyridine); Thiourea; Benzoyl; Crystal structures; Hydrogen bonding; Plane deviation
1. Introduction
studies on oxygen containing thioureas [8±14] that
feature intramolecular NH´´´O hydrogen bonding, as
well as N0H´´´S intermolecular hydrogen bonding.
However, the structure of N-(2-pyridyl)-N0-
benzoylthiourea, PyTubenzo, Fig. 1, has to our knowl-
edge not been reported although a recent report of its
reaction with copper(II) chloride has appeared [15].
The structure of the resulting chloride-bridged one-
dimensional copper(II) polymer included in that
report shows that the thiourea is cyclized at the
pyridine nitrogen and coordination is via the
resulting imine ring nitrogen. We report here the
structures of N,N0-bis(4,6-lutidyl)thiourea and
(4,6Lut)2Tu, N,N0-bis(5-picolyl)thiourea, (5Pic)2Tu
in addition to N-(2-pyridyl)-N0-benzoylthiourea,
PyTubenzo, Fig. 1.
A recent report of the preparation of N,N0-bis(2-
pyridyl)thiourea, (Py)2Tu, and the structures of its
copper(I) and zinc(II) complexes, [Cu(Py2Tu)2]ClO4
and [Zn(Py2Tu)2](ClO4)2 has appeared0 [1]. This
prompted us to include representative N,N -bis(substi-
tuted 2-pyridyl)thioureas in our studies of the struc-
tures and intramolecular and intermolecular hydroge0n
bonding
interactions
of
N-(2-pyridyl)-N -
arylthioureas with substituents on either or both
rings [2±7]. Further, there have been a number of
* Corresponding author. Tel.: 11-206-616-4213; fax: 11-206-
685-8665.
E-mail address: westdx@chem.washington.edu (D.X. West).
0022-2860/02/$ - see front matter q 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-2860(01)00655-X

10
W. Kaminsky et al. / Journal of Molecular Structure 605 (2002) 9±15
Fig. 1. Representations of (4,6Lut)2Tu, (5Pic)2Tu and PyTubenzo showing expected intramolecular hydrogen bonding.
Table 1
Crystallographic data and methods of data collection, solution and re®nement for (4,6Lut)2Tu, (5Pic)2Tu and PyTubenzo
Crystal data
(4,6Lu)2Tu
C15H18N4S
Colorless, prism
0:30 £ 0:25 £ 0:07
Triclinic
(5Pic)2Tu
PyTubenzo
C13H11ON3S
Colorless, prism
0:20 £ 0:14 £ 0:10
Monoclinic
P21/n
Empirical formula
Crystal color, habit
Crystal size (mm)
Crystal system
Space group
C13H14N4S
Colorless, prism
0:25 £ 0:18 £ 0:06
Monoclinic
P21/c
P-1
Ê
a (A)
Ê
b (A)
Ê
c (A)
7.4930(8)
8.7210(8)
12.6040(14)
93.437(5)
94.919(5)
110.246(5)
766.35(14)
2
17.205(2)
5.345(3)
4.4970(5)
17.425(2)
20.243(6)
11.808(2)
a (8)
b (8)
g (8)
117.763(5)
90.23(3)
Ê 3
Volume (A )
1272.6(3)
4
1290.8(1)
4
Z
Formula weight
Density (calculated) (g/cm3)
Absorption coef®cient (mm21)
F(000)
286.39
258.34
257.3
1.241
0.207
1.348
0.242
1.324
0.242
272
544
536
Re¯ections for indexing
Index ranges
91
95
25
27 # h # 7
28 # k # 8
212 # l # 12
2975
219 # h # 20
25 # k # 8
220 # l # 18
3841
0 # h # 6
0 # k # 26
215 # l # 20
3495
Re¯ections collected
Independent re¯ections
Absorption correction
Goodness-of-®t
1614 ꢀRint ˆ 0:0316†
HKL-Scalepack
1.047
2166 ꢀRint ˆ 0:0658†
HKL-Scalepack
0.889
2944 ꢀRint ˆ 0:0491†
C-scan
1.074
Ê 23)
Largest diff. peak (eA
Largest diff. hole (eA
0.224
2 0.196
0.212
2 0.185
0.249
Ê 23)
2 0.280
0.0604, 0.0882
0.1518, 0.1322
R1, wR2
0.0432, 0.1129
0.0611, 0.1227
0.0486, 0.1039
0.1200, 0.1275
R1, wR2 (all re¯ections)

W. Kaminsky et al. / Journal of Molecular Structure 605 (2002) 9±15
11
Table 2
Selected bond distances (A) and angles (8) for (4,6Lut)2Tu,
(5Pic)2Tu and PyTubenzo
Ê
Ê
Distances (A) (4,6Lut)2Tu (5Pic)2Tu PyTubenzo
S1±C7
N1±C2
N1±C6
C2±N2
N2±C7
N3±C7
N3±C8
C8±N4
N4±C12
1.677(3)
1.328(4)
1.347(4)
1.399(4)
1.363(4)
1.337(4)
1.415(4)
1.328(4)
1.337(4)
1.674(3)
1.334(2)
1.346(4)
1.404(4)
1.371(4)
1.341(4)
1.413(4)
1.658(3)
1.325(5)
1.343(6)
1.417(4)
1.329(4)
1.382(4)
1.388(4)
1.326(4) 1.220(4) (C8±O1)
1.344(4) 1.470(5) (C8±C9)
Fig. 2. ORTEP diagram of (4,6Lut)2Tu with atom numbering
scheme and displacement ellipsoids at 50% probability level.
Angles (8)
C2±N1±C6
N1±C2±C3
N1±C2±N2
N2±C2±C3
C2±N2±C7
S1±C7±N2
N2±C7±N3
S1±C7±N3
C7±N3±C8
N3±C8±C9
N3±C8±N4
N4±C8±C9
117.7(3)
116.8(3)
117.0(4)
123.4(3)
117.9(3)
118.7(3)
131.9(3)
117.8(2)
116.4(3)
125.7(2)
131.0(3)
124.2(3)
112.1(3)
123.7(3)
122.4(3)
119.0(3)
118.6(3)
131.8(3)
118.0(2)
114.9(3)
127.1(3)
131.2(3)
126.7(3)
111.1(3)
122.2(3)
116.9(3)
123.2(4)
2. Experimental
109.9(3)
126.9(4)
133.1(3)
Representative of the preparative method for the
bis(2-pyridyl)thioureas is the following: 2-amino-4,6-
lutidine (2-amino-4,6-dimethylpyridine) (6.085 g,
49.9 mmol, Aldrich) and carbon disul®de (2.26 g,
29.7 mmol, Aldrich) were re¯uxed in 50 ml of MeOH
for 8 h. The solution was slowly evaporated to about
20 ml, the white solid ®ltered off in vacuo, and the
resulting solid (4,6Lut)2Tu dried at 358C, yield ˆ
17%; mp ˆ 218±2198C; (5Pic)2Tu, yield ˆ 23%;
mp ˆ 188±1898C: PyTubenzo was prepared by mixing
equimolar amounts (0.001 mol) of 2-aminopyridine
(0.094 g, Aldrich) and benzoyl isothiocyanate
(0.163 g, Aldrich) in 40 ml of 95% EtOH. The solution
was gently heated (ca. 508C) and stirred for 2 h, the
volume reduced to about 20 ml and the white solid
®ltered off in vacuo and dried at 358C, yield, 44%.
Prismatic crystals of the thioureas were grown
by slow evaporation of acetone±ethanol solutions
126.8(3)
114.7(3)
118.6(3)
128.5(3)
116.8(3)
121.5(3) (N3±C8±O1)
121.7(3) (C9±C8±O1)
C8±N4±C12 117.6(2)
(1:1 by volume) at room temperature. Crystals
were mounted on glass ®bers and used for data
collection at 293 K on a
{(4,6Lut)2Tu and (5Pic)2Tu} or Nonius MACH3
Nonius CCD
(PyTubenzo) automatic diffractometer, Mo Ka
ꢀ
ꢀl ˆ 0:71073 A†: Cell constants and an orientation
matrix for data collections were obtained by least
squares re®nements of the diffraction data from 25
re¯ections for PyTubenzo. The structures were
solved with direct methods and missing atoms
were found by difference-Fourier synthesis. All
non-hydrogen atoms were re®ned with anisotropic
temperature factors and hydrogens attached to
nitrogens were found on the difference map. The
H atoms on carbons in PyTubenzo were ®xed at
ꢀ
d ˆ 0:96 A; allowed to ride on the C atoms and
assigned ®xed isotropic temperature factor, U ˆ
ꢀ 2
0:05 A : The coordinates of the H atoms attached
to N and N0 and hydrogens on carbons in
(4,6Lut)2Tu and (5Pic)2Tu were re®ned isotropi-
cally. Re®nement of the structures was made by
full-matrix least-squares on F2. Scattering factors
Fig. 3. ORTEP diagram of (5Pic)2Tu with atom numbering scheme
and displacement ellipsoids at 50% probability level.

12
W. Kaminsky et al. / Journal of Molecular Structure 605 (2002) 9±15
Table 3
Intramolecular and intermolecular hydrogen bond distances (A) and angles (8) for (4,6Lut)2Tu, (5Pic)2Tu and PyTubenzo
Ê
D
A
D±H
H´´´A
D±H´´´A
/(D±H´´´A)
Intramolecular thiourea
(4,6Lut)2Tu
(5Pic)2Tu
N3
N3
N2
N1
N1
O1
0.850(3)
0.82(3)
0.88(3)
1.961(3)
1.99(3)
1.89(3)
2.666(4)
2.666(4)
2.598(4)
139.7(2)
139.6(29)
136(3)
PyTubenzo
Intermolecular thiourea
(4,6Lut)2Tu
(5Pic)2Tu
N2
S1
S1
S1
0.871(3)
0.88(3)
0.91(3)
2.540(1)
2.62(3)
2.71(3)
3.393(3)
3.474(3)
3.587(3)
166.6(2)
165.0(23)
161(3)
N2
N3
PyTubenzo
are from Wassmaire and Kirfel [16], calculations
were done by maXus, version 2.0 [17], and
graphics are Platon for Windows [18].
intramolecular
N3±H3´´´N1
interactions
of
(4,6Lut)2Tu and (5Pic)2Tu are equivalent, but the
intermolecular N2±H2´´´S1 interactions are different.
The bulkier (4,6Lut)2Tu has a shorter N2´´´S1 non-
bonding distance, as well as a shorter H2´´´S1
distance. The intramolecular hydrogen bonding inter-
action of (4,6Lut)2Tu is substantially weaker than
found for 4,6LutTuPh [14]; H3´´´N1 distance is
3. Results and discussion
3.1. Structural studies of (4,6Lut)2Tu and (5Pic)2Tu
Ê
1.961(3) A and the N3±H3´´´N1 distance and angle
Ê
are 2.666(4) A and 139.7(2)8 for (4,6Lut)2Tu
Ê
compared to 1.83(4), 2.633(4) A and 152(3)8 for
4,6LutTuPh [7]. However, the intermolecular interac-
tion of (4,6Lut)2Tu is stronger than 4,6LutTuPh, the
H2´´´S1 and N2´´´S1 distances are 2.540(1), 3.393(3)
Ê
and 2.66(4), 3.462(3) A, respectively. In contrast,
(5Pic)2Tu has a longer H2´´´S1 distance and N2´´´S1
non-bonding distance than 5PicTuPh, an average of
Ê
2.62(3), 3.474(3) A for the former compared to 2.47,
Ê
3.433(7) A for the latter, but their intramolecular
The crystallographic data, as well as the solution
and re®nement information for these thioureas, are
shown in and Table 1, and the atomic coordinates
and equivalent isotropic displacement coef®cients
are included in the deposited material (CCDC), as
are a complete list of bond distances and angles
(Table 2, Figs. 2 and 3).
There are no signi®cant differences in the bond
distances of (4,6Lut)2Tu and (5Pic)2Tu (Table 2); all
distances are within twice their combined estimated
standard deviations. N2±C7 is longer than C7±N3 by
interactions are essentially equivalent. The N2±
H2´´´S1 angles are also different; ꢀ5Pic†2Tu ˆ
165:0ꢀ23†8 and 5PicTuPh averages 156.18.
Ê
0.02±0.03 A, which is probably due to N2±C7 being
involved in the ring resulting from N3±H3´´´N1
hydrogen bonding. There are small differences in a
few of the bond angles between the two; the largest
difference involves N3±C8±C9.
A comparison of the bond distances of (5Pic)2Tu to
N-(5-picolyl)-N0-phenyl thiourea, 5P0icTuPh [14], and
(4,6Lut)2Tu to N-(4,6-lutidyl)-N -phenylthiourea,
4,6LutTuPh [14], shows no signi®cant differences
for either pair of compounds. Similarly, the bond
angles in the two pairs of compounds are within
twice their combined e.s.d. values.
The most signi®cant difference between
(4,6Lut)2Tu and (5Pic)2Tu is their planarity; the
angle between the two pyridyl rings in (4,6Lut)2Tu
is 24.48(0.82)8 compared to 10.55(0.43)8 for
(5Pic)2Tu (Table 4). The pyridine ring involved in
hydrogen bonding is almost coplanar with the
thiourea moiety in the two compounds, but the other
pyridine ring is signi®cantly out of its plane. The
analogous phenyl derivatives have the following
angles between the mean plane of the pyridyl and
phenyl rings: 13.91(0.17)8 for 4,6LutTuPh and
5PicTuPh averages 28.75(0.97)8. Since the relation-
ship for this angle is 5PicTuPh . 4; 6LutTuPh; but
Like other 2-pyridyl thioureas, these bis(2-pyri-
dyl)thioureas possess intramolecular and intermole-
cular hydrogen bonding interactions, Table 3. The

W. Kaminsky et al. / Journal of Molecular Structure 605 (2002) 9±15
13
Table 4
Mean plane data and angles between planes for (4,6Lut)2Tu, (5Pic)2Tu and PyTubenzo
Compound Plane
Plane # Mean plane deviation Atom with greatest deviation Plane/plane Angle
(4,6Lut)2Tu N1±C2±C3±C4±C5±C6
N2±C7±S1±N3
1
2
3
0.0004
0.0013
0.0008
N1, 0.0031(0.0019)
C7, 0.0078(0.0024)
C12, 0.0177(0.0019)
1/2
2/3
3/1
1.09(0.04)
25.48(0.87)
24.41(0.82)
C8±C9±C10±C11±C12±C13
(5Pic)2Tu
N1±C2±C3±C4±C5±C6
N2±C7±S1±N3
1
2
3
0.0002
0.0002
0.0015
C5, 0.0105(0.0030)
C7, 0.0032(0.0030)
C9, 0.0138(0.0047)
1/2
2/3
3/1
1.15(0.05)
9.50(0.31)
10.35(0.43)
C8±C9±C10±C11±C12±C13
PyTubenzo N1±C2±C3±C4±C5±C6
N2±C7±S1±N3
1
2
3
4
0.0064
0.0030
0.0039
0.0375
C6, 0.0110(0.0044)
C7, 0.0053(0.0029)
C9, 0.0056(0.0025)
N3, 0.0529(0.0025)
1/2
2/3
3/1
3/4
2.09(0.29)
30.34(0.17)
31.74(0.18)
28.59(0.16)
C9±C10±C11±C12±C13±C14
N2±C7±N3±S1±C8±O1
Ê
Tu}2](ClO4)2 are identical and S1±C7 is 1.718(4) A
Ê
and N1±C2 is 1.362(6) A; both are signi®cantly
ꢀ4; 6Lut†2Tu . ꢀ5Pic†2Tu; substitution on the second
ring is a signi®cant factor in the packing of these
molecules.
longer than found for (5Pic)2Tu, 1.677(3) and
Ê
Although bond distances, bond angles and intramo-
lecular hydrogen bonding parameters of bis(2-pyri-
dyl)thioureas are not signi®cantly affected by
position of substitution on the pyridyl rings, intermo-
lecular hydrogen bonding and planarity of the mole-
cules are different. Further, a comparison of the bis(2-
pyridyl)thioureas with their (2-pyridyl)phenylthiourea
analogs [14] shows differences in all of the above
except for bond distances. Based on angles between
the pyridine and tolyl rings of 67.4(1), 79.4(1) and
1.328(4) A, respectively. In addition, N2±C7,
Ê
Ê
1.342(6) A, and N3±C7, 1.356(6) A, in [Zn{(Py)2-
Tu}2](ClO4)2 are different from (5Pic)2Tu, 1.371(4)
Ê
and 1.341(4) A, respectively. Only angles involving
the zinc center are listed and the authors indicate that
no hydrogen bonding is present in [Zn{(Py)2-
Tu}2](ClO4)2 [1]. Consistent with the lower charge
on the metal center in [Cu{(Py)2Tu}2]ClO4, the S1±
C7 and N1±C2 distances are essentially the same as
those of (5Pic)2Tu. However, N2±C7 and N3±C7 are
substantially different and have essentially the same
distances as found for [Zn{(Py)2Tu}2](ClO4)2 [1]. The
ligands in the copper(I) complex show N2±H2´´´N4
hydrogen bonding interactions with H´´´N distances
58.7(1)8
PyTuoT; N-(2-pyridyl)-N0-m-tolylthiourea, PyTumT
and PyTupT,
N-(2-pyridyl)-N0-p-tolylthiourea,
for
N-(2-pyridyl)-N0-o-tolylthiourea,
compared to the angles for 5PicTuPh and 4,6LutTuPh
[14], it was suggested that substitution on the
hydrogen bonding pyridine ring increased the
planarity of the molecule, but substitution on the
phenyl ring decreased the planarity [3]. The greater
substitution on the pyridine ring not involved in
hydrogen bonding in (4,6Lut)2Tu compared
(5Pic)2Tu may help to explain the larger angle
between the mean planes of the pyridine rings.
Since bond distances, bond angles and intramole-
cular hydrogen bonding are not signi®cantly different
in (4,6Lut)2Tu and (5Pic)2Tu, it is reasonable to
compare these parameters to the coordinated
(Py)2Tu in the complexes [Cu{(Py)2Tu}2]ClO4 and
[Zn{(Py)2Tu}2](ClO4)2 [1]. In both complexes, the
coordination of (Py)2Tu is via a pyridine nitrogen
and the thione sulfur. The two ligands in [Zn{(Py)2-
Ê
of 1.972 and 1.894 A, which is shorter than the
Ê
1.99(3) A found for (5Pic)2Tu. Therefore, the forma-
tion of the chelate ring and the hydrogen bonding
interaction with the second pyridine ring in Cu{(Py)2-
Tu}2]ClO4 cause the difference in N2±C7 and N3±C7
distances. Bond angles that would allow a comparison
between the coordinated and non-coordinated
thioureas are not listed [1]. The planes of the two
pyridine rings in a ligand are at an angle of 9.288,
which is similar to 10.35(0.43)8 found for (5Pic)2Tu.
3.2. Structural studies of PyTubenzo
Like the bis(2-pyridyl)thioureas PyTubenzo crys-
tallized with one unique molecule in the unit cell,
(Fig. 4). The intramolecular hydrogen bonding is

14
W. Kaminsky et al. / Journal of Molecular Structure 605 (2002) 9±15
benzo to be cyclized at the pyridine nitrogen resulting
in a thiadiazole ring and coordination of the ring's
imine nitrogen [15]. Also, N3±C7 formally becomes
a double bond so that bond distances for what was the
thiourea moiety should undergo signi®cant change.
N2±C7, formally a single bond in both, is not signi®-
Ê
cantly different, 1.341(4) A in PyTubenzo and
Ê
1.334(8) A in the complex. However, N3±C7
Ê
decreases from 1.387(7) to 1.356(8) A, consistent
with the complex having greater double bond char-
acter, but still is longer than N2±C7, which is
formally a single bond [15]. No other information is
provided that allows comparison between PyTubenzo
and the cyclized ligand in the copper(II) complex.
Fig. 4. ORTEP diagram of PyTurbenzo with atom numbering
acheme and displacement ellipsoids at 50% probability level.
4. Supplementary material
between N2H2 and the benzoyl oxygen and the
Ê
nonbonding N2´´´O1 distance, 2.598(4) A, is shorter
Crystallographic data (excluding structure factors)
for the structures reported in this paper have been
deposited with the Cambridge Crystallographic Data
Center as supplementary publication no CCDC-
157695 for (4,6Lut)2Tu, CCDC-157694 for
(5Pic)2Tu, and CCDC-154846 for PyTubenzo. Copies
of available material can be obtained, free of charge,
on application to the Director, CCDC, 12 Union Road,
Cambridge CB21EZ, UK (fax: 144-1223-336033 or
e-mail: deposit@ccdc.cam.ac.uk).
than the N2´´´N1 distance of the bis(2-pyri-
dyl)thioureas indicating a stronger interaction. This
distance is also shorter than the N´´´O distance
found
2.635(3) A [12] and N-benzoyl-N -p-methoxyphe-
for
Ê
N-benzoyl-N0-p-nitrophenylthiourea,
0
Ê
nylthiourea, 2.618(9) A [13]. The N2±H2´´´O angle
of PyTubenzo is smaller than the N3±H3´´´N1 angle
of (4,6Lut)2Tu and (5Pic)2Tu, as is the intermolecular
angle of N3H3´´´S1 compared to N2H2´´´S1 for the
bis(2-pyridyl)thioureas. The intermolecular hydrogen
bonding for PyTubenzo, however, appears to be
weaker compared to the bis(2-pyridyl)thioureas
based on longer N3H3´´´S1 nonbonding distance.
There are small differences in the bond distances in
the thiourea moiety of PyTubenzo compared to the
bis(2-pyridyl)thioureas. The difference in N2±C7
References
[1] Y. Fan, H. Lu, H. Hou, Z. Zhou, Q. Zhao, L. Zhang, F. Cheng,
J. Coord. Chem. 50 (2000) 65.
Â
[2] D.X. West, A.K. Hermetet, L.J. Ackerman, J. Valdes-
 Â
Martõnez, S. Hernandez-Ortega, Acta Cryst. C55 (1999) 811.
Â
Â
Â
[3] J. Valdes-Martõnez, S. Hernandez-Ortega, D.X. West, L.J.
Ackerman, J.K. Swearingen, A.K. Hermetet, J. Mol. Struct.
478 (1999) 219.
Ê
and N3±C7 bond distances, .0.05 A, is larger for
PyTubenzo than the bis(2-pyridyl)thioureas; the elec-
tron withdrawing effect of the carbonyl group
increases this difference. The angles about the thiose-
micarbazone moiety are similar to those of the bis(2-
pyridyl)thioureas based on the hydrogen bonding
patterns. Although not involved in intramolecular
hydrogen bonding like other 2-pyridyl thioureas, the
pyridine ring is nearly coplanar with the thiourea
moiety, but the phenyl ring is at a larger angle to
the thiourea moiety.
[4] D.X. West, J.K. Swearingen, A.K. Hermetet, L.J. Ackerman,
C. Presto, J. Mol. Struct. 522 (2000) 27.
[5] D.X. West, J.K. Swearingen, A.K. Hermetet, L.J. Ackerman,
J. Mol. Struct. 562 (2001) 95.
[6] L.F. Szczepura, K.K. Eilts, A.K. Hermetet, L.J. Ackerman,
J.K. Swearingen, D.X.West, J. Mol. Struct., in press.
Â
Â
Â
Â
[7] J. Valdes-Martõnez, S. Hernandez-Ortega, G. Espinosa-Perez,
C.A. Presto, A.K. Hermetet, K.D. Haslow, L.J. Ackerman,
L.F. Szczepura, J.M. Giesen, K.I. Goldberg, W. Kaminsky,
D.X. West, J. Mol. Struct., submitted for publication.
[8] A. Dago, M.A. Simonov, E.A. Pobedimskaya, A. Macias, A.
Â
Martõn, Kristallogra®ya 32 (1987) 1024.
Reaction with copper(II) chloride causes PyTu-

W. Kaminsky et al. / Journal of Molecular Structure 605 (2002) 9±15
15
[9] A. Dago, M.A. Simonov, E.A. Pobedimskaya, A. Macias, A.
Â
Martõn, Kristallogra®ya 33 (1988) 1021.
[14] S.S.S. Raj, L. Puviarasan, D. Velmurugan, G. Jayanthi, H.J.-
K. Fun, Acta Cryst. C55 (1999) 1318.
Â
[10] A. Dago, Y. Shepelev, F. Fajardo, F. Alvarez, R. Pomes, Acta
[15] D.-J. Che, G. Li, Z. Yu, D.-P. Zou, C.-X. Du, Inorg. Chem.
Commun. 3 (2000) 537.
Cryst. C45 (1989) 1192.
[11] K.R. Koch, C. Sacht, S. Bourne, Inorg. Chim. Acta 232 (1995)
109.
[16] D. Wassmaier, A. Kirfel, Acta Cryst. A51 (1995) 416.
[17] S. Mackay, C. Edwards, A. Henderson, C. Gilmore, N.
Stewart, K. Shankland, A. Donald, maxus, version 2, Univer-
sity of Glascow, Scotland, 1997.
[12] D.-C. Zhang, Y.-Q. Zhang, Y. Cao, B. Zhao, Acta Cryst. C52
(1996) 1716.
[13] Y. Cao, B. Zhao, Y.-Q. Zhang, D.-C. Zhang, Acta Cryst. C52
(1996) 1772.
[18] A.L. Spek, platon: A Multipurpose Crystallographic Tool,
Utrecht University, Utrecht, The Netherlands, 1999.